Metallic-pigment composition

ABSTRACT

Provided is a metallic-pigment composition which is usable in coating compositions or ink compositions, in particular, in water-based coating compositions or aqueous inks, and which gives coating compositions having excellent storage stability. The metallic-pigment composition gives a coating film having excellent performances with respect to brightness, hiding properties, flip-flop feeling, etc., causes no colorant or organic-pigment discoloration, and has excellent adhesion and chemical resistance. The metallic-pigment composition comprises one or more mixed-coordination-type heteropolyanion compounds, a hydrolyzate of a silicon compound and/or a condensate thereof, and metal particles.

TECHNICAL FIELD

The present invention relates to a metallic pigment composition suitablefor coating compositions, ink compositions or the like, in particular,water-based coatings, water-based inks or the like.

BACKGROUND ART

Conventionally, metallic pigments have been used for metallic coatingsand printing inks, for kneading into plastic, and the like for thepurpose of achieving a decorative effect with a focus on metallicfeeling.

Recently, in the field of coatings, in view of resource saving andanti-pollution, there has been an increasing need for conversion towater-based coatings in which the amount of an organic solvent used issmall, but there are still few examples of water-based coatings whichare practicable in metallic coatings containing a metallic pigment. Thereason for this is that metallic pigments are easily corroded inwater-based coatings. In the case where metal powders are present inwater-based coatings, the metal powders are corroded by water in anacidic, neutral or basic region, or in multiple regions of themdepending on the nature of each metal, thereby generating a hydrogengas. This is an extremely serious safety problem during productionprocesses of coatings and inks in paint manufacturers and inkmanufacturers as well as during processes of coatings and prints inautomobile manufacturers, home appliance manufacturers and printingcompanies. The corrosion resistance of metallic pigments in water,water-based coatings or water-based inks is, hereinafter, referred to as“storage stability”.

Patent Document 1 discloses an aluminum pigment having an inorganicmolybdenum coating film, and also a coating film made of amorphoussilica, which covers the inorganic molybdenum coating film.

In addition, Patent Document 2 discloses an aluminum pigment having aninorganic molybdenum coating film and also a coating film made ofamorphous silica and/or a coating film formed from a silane couplingagent, which covers the inorganic molybdenum coating film.

However, in any of these patent documents, the deterioration in colortone of the metallic pigment is not avoidable, and the processes thereinare also complicated.

In order to simultaneously achieve storage stability in water-basedcoatings or water-based inks and the maintenance of the color tone of ametallic pigment in them, Patent Document 3 discloses a metallic pigmentcontaining an amine salt of molybdic acid and Patent Document 4discloses a metallic pigment containing an amine salt of heteropolyacid.

However, in any of these patent documents, storage stability isinsufficient. In addition, in any of these patent documents, there is adisadvantage that a dye or an organic pigment in coatings is partiallydiscolored in the case where it is blended with the coatings.Furthermore, in some applications, a coating film obtained by using themetallic pigment is often required to have adhesion and chemicalresistance such as acid resistance or alkali resistance.

CITATION LIST Patent Literature

-   Patent Document 1: JP 2003-147226 A-   Patent Document 2: WO 2004/096921-   Patent Document 3: JP 2007-169613 A-   Patent Document 4: WO 2008/059839 A

SUMMARY OF INVENTION Technical Problem

An object of the present invention is to provide a metallic pigmentcomposition that has overcome the above disadvantages of the prior art,namely to provide a metallic pigment composition that can be used incoating compositions, ink compositions or the like, in particular,water-based coatings, water-based inks or the like, that is excellent instorage stability of coatings, that has performances excellent inphotoluminescence, hiding power, flip-flop feeling and the like whenforming a coating film, and that does not allow a dye or an organicpigment to discolor.

Another object is to provide a metallic pigment composition that isexcellent in adhesion and chemical resistance when forming a coatingfilm, in addition to the above performances.

Solution to Problem

The present inventors have found that the above problems can be solvedby using a metallic pigment composition containing a mixed-coordinationtype heteropolyanion compound; a hydrolysate of a silicon-containingcompound and/or a condensate thereof; and metallic particles, therebyachieving the present invention.

Namely, the present invention is as follows.

(1) A metallic pigment composition containing one or moremixed-coordination type heteropolyanion compounds, a hydrolysate of asilicon-containing compound and/or a condensate thereof, and metallicparticles.(2) The metallic pigment composition according to (1), furthercontaining an organic oligomer or polymer.(3) The metallic pigment composition according to (1) or (2), furthercontaining at least one selected from the group consisting of (i)inorganic phosphoric acids or salts thereof, and (ii) acidic organicphosphoric or phosphorous acid esters or salts thereof.(4) The metallic pigment composition according to any one of (1) to (3),wherein the metallic particles are made of aluminum.(5) The metallic pigment composition according to any one of (1) to (4),wherein a heteroatom constituting the mixed-coordination typeheteropolyanion compound is at least one selected from elements of GroupIIIB, Group IVB, and Group VB.(6) The metallic pigment composition according to (5), wherein theelements of Group IIIB, Group IVB, and Group VB are B, Si, and P.(7) The metallic pigment composition according to any one of (1) to (6),wherein a polyatom constituting the mixed-coordination typeheteropolyanion compound is selected from transition metals.(8) The metallic pigment composition according to (7), wherein thetransition metals are Ti, Zr, V, Nb, Mo, and W.(9) The metallic pigment composition according to any one of (1) to (4),wherein the mixed-coordination type heteropolyanion compound is at leastone selected from H₃PW_(x)Mo_(12-x)O₄₀.nH₂O (phosphotungstomolybdicacid.n-hydrate), H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O (phosphovanadomolybdicacid.n-hydrate), H₄SiW_(x)Mo_(12-x)O₄₀.nH₂O (silicotungstomolybdicacid.n-hydrate), and H_(4+x)SiV_(x)Mo_(12-x)O₄₀.nH₂O(silicovanadomolybdic acid.n-hydrate); and 1≦x≦11 and n≧0.(10) The metallic pigment composition according to any one of (1) to(8), wherein the mixed-coordination type heteropolyanion compound is asalt of a mixed-coordination type heteropoly acid with at least oneselected from the group consisting of alkali metals, alkaline earthmetals, and ammonia.(11) The metallic pigment composition according to (10), wherein themixed-coordination type heteropoly acid is the mixed-coordination typeheteropoly acid according to (9).(12) The metallic pigment composition according to any one of (1) to(8), wherein the mixed-coordination type heteropolyanion compound is asalt of a mixed-coordination type heteropoly acid with at least oneselected from amine compounds represented by the following generalformula (1):

wherein R1, R2 and R3 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R1 and R2 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, or are taken together with a nitrogen atom to form a 5-memberedor 6-membered ring that is capable of additionally containing a nitrogenor oxygen atom as a crosslinking member, or R1, R2 and R3 are takentogether to form a multi-membered multiring composition that is capableof containing one or more additional nitrogen atoms and/or oxygen atomsas a crosslinking member, and R1, R2 and R3 are not a hydrogen atom atthe same time; and n represents a numerical value of 1 to 2.(13) The metallic pigment composition according to (12), wherein themixed-coordination type heteropoly acid is a mixed-coordination typeheteropoly acid according to (9).(14) The metallic pigment composition according to any one of (1) to(13), wherein the silicon-containing compound is at least one selectedfrom compounds represented by the following general formula (2), (3),(4) or (5) and a partial condensate thereof:

[Formula 2]

R4mSi(OR5)4-m  (2)

wherein R4 is a hydrogen atom or a hydrocarbon group having 1 to 30carbon atoms that may optionally contain a halogen group, R5 is ahydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R4 andR5 may be the same or different, and when the numbers of R4 and R5 areeach two or more, each of R4 and R5 may be the same, may be partiallythe same, or may be all different; and 1≦m≦3;

[Formula 3]

R6pR7qSi(OR8)4-p-q  (3)

wherein R6 is a group containing a reactive group that can be chemicallybound to other functional group, R7 is a hydrogen atom or a hydrocarbongroup having 1 to 30 carbon atoms that may optionally contain a halogengroup, R8 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbonatoms, and when the numbers of R6, R7 and R8 are each two or more, eachof R6, R7 and R8 may be the same, may be partially the same, or may beall different; and 1≦p≦3, 0≦q≦2, and 1≦p+q≦3;

[Formula 4]

Si(OR9)4  (4)

wherein R9 is a hydrogen atom or a hydrocarbon group having 1 to 8carbon atoms, and when the number of R9 is two or more, each of R9 maybe the same, may be partially the same, or may be all different; and

[Formula 5]

R10rSiCl4-r  (5)

wherein R10 is a hydrogen atom or a hydrocarbon group having 1 to 30carbon atoms that may optionally contain a halogen group, and when thenumber of R10 is two or more, each of R10 may be the same, may bepartially the same, or may be all different; and 0≦r≦3.(15) The metallic pigment composition according to any one of (2) to(14), wherein the organic oligomer or polymer is an acrylic resin and/ora polyester resin.(16) The metallic pigment composition according to any one of (3) to(15), wherein the inorganic phosphoric acids are at least one selectedfrom orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid,triphosphoric acid, tetraphosphoric acid, and phosphorous acid.(17) The metallic pigment composition according to any one of (3) to(15), wherein the inorganic phosphoric acid salts are salts of theinorganic phosphoric acids with at least one selected from alkalimetals, alkaline earth metals, ammonia, and amines represented by thefollowing general formula (6):

wherein R11, R12 and R13 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R11 and R12 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, R11 and R12 are optionally taken together with a nitrogen atom toform a 5-membered or 6-membered ring that is capable of additionallycontaining a nitrogen or oxygen atom as a crosslinking member, or R11,R12 and R13 are optionally taken together to form a multi-memberedmultiring that is capable of containing one or more additional nitrogenatoms and/or oxygen atoms as a crosslinking member, and R11, R12 and R13are not a hydrogen atom at the same time; and n represents a numericalvalue of 1 to 2.(18) The metallic pigment composition according to any one of (3) to(15), wherein the acidic organic phosphoric or phosphorous acid estersare at least one selected from compounds represented by the followinggeneral formula (7):

wherein R14, R15 and R16 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, or a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, one or twoof R14, R15 and R16 are a hydrogen atom, and the total number of carbonatoms of R14, R15 and R16 is 4 or more; and m represents a numericalvalue of 0 or 1.(19) The metallic pigment composition according to any one of (3) to(15), wherein the acidic organic phosphoric or phosphorous acid estersalts are salts of phosphoric acid esters represented by the followinggeneral formula (7) with at least one selected from alkali metals,alkaline earth metals, ammonia, and amines represented by the followinggeneral formula (6):

wherein R14, R15 and R16 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, or a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, one or twoof R14, R15 and R16 are a hydrogen atom, and the total number of carbonatoms of R14, R15 and R16 is 4 or more; and m represents a numericalvalue of 0 or 1; and

wherein R11, R12 and R13 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R11 and R12 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, R11 and R12 are optionally taken together with a nitrogen atom toform a 5-membered or 6-membered ring that is capable of additionallycontaining a nitrogen or oxygen atom as a crosslinking member, or R11,R12 and R13 are optionally taken together to form a multi-memberedmultiring that is capable of containing one or more additional nitrogenatoms and/or oxygen atoms as a crosslinking member, and R11, R12 and R13are not a hydrogen atom at the same time; and n represents a numericalvalue of 1 to 2.(20) The metallic pigment composition according to any one of (2) to(19), wherein a monomer constituting the organic oligomer or polymer isat least one selected from compounds represented by the followinggeneral formula (8):

wherein R17, R18 and R19 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, or a grouprepresented by the following general formula (9), one or two of R17, R18and R19 are a hydrogen atom, one or two thereof are the followinggeneral formula (9), and the total number of carbon atoms of R17, R18and R19 is 4 or more; and m represents a numerical value of 0 or 1:

wherein R20 and R23 represent a hydrogen atom or a methyl group, R21 isa trivalent organic group having 2 to 8 carbon atoms that may optionallycontain an oxygen atom, and R22 represents a hydrogen atom or thefollowing general formula (10); and h represents a numerical value of 0or 1 and i represents a numerical value of 0 to 10:

[Formula 12]

—CH²X  (10)

wherein X represents a hydrogen atom or a chlorine atom.(21) The metallic pigment composition according to any one of (1) to(20), wherein the mixed-coordination type heteropolyanion compound ispresent in an amount of 0.01 to 10 parts by weight based on 100 parts byweight of the metallic particles.(22) The metallic pigment composition according to any one of (1) to(21), wherein the hydrolysate of a silicon-containing compound and/orthe condensate thereof is present in an amount of 0.01 to 50 parts byweight based on 100 parts by weight of the metallic particles.(23) The metallic pigment composition according to any one of (2) to(22), wherein the organic oligomer or polymer is present in an amount of0.01 to 50 parts by weight based on 100 parts by weight of the metallicparticles.(24) The metallic pigment composition according to any one of (3) to(23), containing at least one selected from the group consisting of (i)inorganic phosphoric acids or salts thereof; and (ii) acidic organicphosphoric or phosphorous acid esters or salts thereof in an amount of0.01 to 20 parts by weight based on 100 parts by weight of the metallicparticles.(25) A method for producing the metallic pigment composition accordingto any one of (1) to (24), including mixing metallic particles with amixed-coordination type heteropolyanion compound and a hydrolysate of asilicon-containing compound and/or a condensate thereof in the presenceof a solvent in separate steps or in a single step.(26) The production method according to (25), including mixing themetallic particles with the mixed-coordination type heteropolyanioncompound in the presence of a solvent, and then mixing the resultingmixture with the hydrolysate of a silicon-containing compound and/or thecondensate thereof.(27) A method for producing the metallic pigment composition accordingto any one of (2) to (24), including mixing metallic particles with amixed-coordination type heteropolyanion compound and a hydrolysate of asilicon-containing compound and/or a condensate thereof in the presenceof a solvent in separate steps or in a single step, and thenpolymerizing or mixing an organic oligomer or polymer.(28) A coating composition containing the metallic pigment compositionaccording to any one of (1) to (24).(29) An ink composition containing the metallic pigment compositionaccording to any one of (1) to (24).(30) A coating film formed by the coating composition according to (28)or being coated with the coating composition according to (28).(31) A printed material formed by the ink composition according to (29).

In the case where the metallic pigment composition of the presentinvention is used in coating compositions, ink compositions or the like,in particular water-based coatings, water-based inks or the like, ametallic pigment composition can be obtained that is excellent instorage stability, and excellent in photoluminescence, hiding power,flip-flop feeling and the like when forming a coating film, and thatdoes not allow a dye or an organic pigment to discolor. A metallicpigment composition can also be obtained that is excellent in adhesionand chemical resistance when forming a coating film, in addition to theabove performances.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present invention will be described in detail withreference to, in particular, preferable aspects of the presentinvention.

As metallic particles for use in the present invention, particles ofbase metals such as aluminum, zinc, iron, magnesium, copper and nickel,and particles of alloys thereof can be preferably used.

With respect to the shape thereof, the average particle diameter (d50)is 2 to 40 μm, the average thickness (t) is preferably in a range of0.001 to 10 μm and further preferably in a range of 0.01 to 10 and theaverage aspect ratio is preferably in a range of 1 to 2500. Herein, theaverage aspect ratio means a value obtained by dividing the averageparticle diameter (d50) of the metallic particles by the averagethickness (t).

In the case where the metallic particles are used as a pigment,scale-like particles are preferable.

Particularly suitable are aluminum flakes frequently used as a pigmentfor metallic coatings. As aluminum flakes for use in the presentinvention, suitable are those having surface texture, particle diameterand shape which are demanded for the pigment for metallic coatings, suchas surface glossiness, whiteness and photoluminescence.

Aluminum flakes are usually commercially available in the state of apaste, and may be used as they are or may be used after fatty acid andthe like on the surface thereof are removed in advance by an organicsolvent and the like. So-called aluminum-deposited foils can also beused in which the average particle diameter (d50) is 3 to 30 μm and theaverage thickness (t) is 5 to 50 nm.

A mixed-coordination type heteropolyanion of a mixed-coordination typeheteropolyanion compound for use in the present invention is one havinga structure in which some of polyatoms of a heteropolyanion consistingof one element are substituted with other elements, and exhibitingdifferent physical properties from a mixture of the respectiveheteropolyanions.

In the case where the mixed-coordination type heteropolyanion isrepresented by a chemical formula, [X_(p)M_(q)N_(r)O_(s)]^(t), theheteropolyanion is represented by [X_(p)M_(q)O_(s)]^(t), and is alsodistinguished from an isopolyanion [M_(q)O_(s)]^(t). Herein, aheteroatom, X, represents elements of Group IIIB, Group IVB, and GroupVB, such as B, Si, Ge, P, and As, and among them, B, Si, and P arepreferable. Polyatoms, M and N, represent transition metals such as Ti,Zr, V, Nb, Mo and W, wherein Ti, Zr, V, Nb, Mo, and W are preferable.

In addition, p, q, r, and s represent the number of atoms and trepresents an oxidation number.

Since a heteropolyanion compound has a large number of structures, themixed-coordination type heteropolyanion compound can have a largernumber of structures. Representative and preferable examples of themixed-coordination type heteropolyanion compound include the followingmixed-coordination type heteropoly acids: H₃PW_(x)Mo_(12-x)O₄₀.nH₂O(phosphotungstomolybdic acid.n-hydrate), H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O(phosphovanadomolybdic acid.n-hydrate), H₄SiW_(x)Mo_(12-x)O₄₀.nH₂O(silicotungstomolybdic acid.n-hydrate), andH_(4+x)SiV_(x)Mo_(12-x)O₄₀.nH₂O (silicovanadomolybdic acid.n-hydrate)(wherein, 1≦x≦11 and n≧0).

Among them, preferable specific examples include mixed-coordination typeheteropoly acids such as H₃PW₃Mo₉O₄₀.nH₂O, H₃PW₆Mo₆O₄₀.nH₂O,H₃PW₉Mo₃O₄₀.nH₂O, H₄PV₁Mo₁₁O₄₀.nH₂O, H₆PV₃Mo₉O₄₀.nH₂O,H₄SiW₃Mo₉O₄₀.nH₂O, H₄SiW₆Mo₆O₄₀.nH₂O, H₄SiW₉Mo₃O₄₀.nH₂O,H₅SiV₁Mo₁₁O₄₀.nH₂O, and H₇SiV₃Mo₉O₄₀.nH₂O (wherein, n≧0).

The mixed-coordination type heteropolyanion compound may be used in theform of an acid (so-called, mixed-coordination type heteropoly acid), ormay be used in the form of a (partial or complete) salt in which aspecified cation serves as a counterion.

Examples of the countercation source in the case of using in the form ofa salt include at least one selected from inorganic components such asalkali metals including lithium, sodium, potassium, rubidium, andcesium; alkaline earth metals including magnesium, calcium, strontium,and barium; metals including manganese, iron, cobalt, nickel, copper,zinc, silver, cadmium, lead, and aluminum; and ammonia; and organiccomponents such as amine compounds. Among the inorganic components,salts of alkali metals, alkaline earth metals, and ammonia arepreferable.

In the case where at least one selected from these alkali metals,alkaline earth metals, and ammonia serves as the countercation source,the mixed-coordination type heteropolyanion compound is more preferablyused in the form of a salt of the countercation source with at least oneof H₃PW_(x)Mo_(12-x)O₄₀.nH₂O (phosphotungstomolybdic acid.n-hydrate),H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O (phosphovanadomolybdic acid.n-hydrate),H₄SiW_(x)Mo_(12-x)O₄₀.nH₂O (silicotungstomolybdic acid.n-hydrate), andH_(4+x)SiV_(x)Mo_(12-x)O₄₀.nH₂O (silicovanadomolybdic acid.n-hydrate).

The amine compounds which are the organic components may also bepreferably used, and specific examples are those represented by thefollowing general formula (1).

(wherein R1, R2 and R3 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, wherein R1 and R2are optionally taken together to form a 5-membered or 6-memberedcycloalkyl group, R1 and R2 are optionally taken together with anitrogen atom to form a 5-membered or 6-membered ring that is capable ofadditionally containing a nitrogen or oxygen atom as a crosslinkingmember, or R1, R2 and R3 are optionally taken together to form amulti-membered multiring composition that is capable of containing oneor more additional nitrogen atoms and/or oxygen atoms as a crosslinkingmember. R1, R2 and R3 are not a hydrogen atom at the same time. nrepresents a numerical value of 1 to 2.)

Specific examples include straight primary amines such as ethylamine,propylamine, butylamine, hexylamine, octylamine, laurylamine,tridecylamine and stearylamine; branched primary amines such asisopropylamine, isobutylamine, 2-ethylhexylamine and branchedtridecylamine; straight secondary amines such as dimethylamine,diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine,dilaurylamine, ditridecylamine and distearylamine; branched secondaryamines such as diisopropylamine, diisobutylamine, di-2-ethylhexylamineand dibranched tridecylamine; asymmetric secondary amines such asN-methylbutylamine, N-ethylbutylamine, N-ethylhexylamine,N-ethyllaurylamine, N-ethylstearylamine, N-isopropyloctylamine andN-isobutyl-2-ethylhexylamine; straight tertiary amines such astrimethylamine, triethylamine, tripropylamine, tributylamine,trioctylamine, trilaurylamine, tritridecylamine and tristearylamine;branched tertiary amines such as triisopropylamine, triisobutylamine,tri-2-ethylhexylamine and tribranched tridecylamine; tertiary amineshaving a mixed hydrocarbon group, such as N,N-dimethyloctylamine,N,N-dimethyllaurylamine, N,N-dimethylstearylamine andN,N-diethyllaurylamine; and additionally, amines having an alkenylgroup, such as allylamine, diallylamine, triallylamine andN,N-dimethylallylamine; and alicyclic primary amines such ascyclohexylamine and 2-methylcyclohexylamine; primary amines having anaromatic ring substituent, such as aniline, benzylamine and4-methylbenzylamine; alicyclic secondary amines such asN,N-dicyclohexylamine and N,N-di-2-methylcyclohexylamine; secondaryamines having an aromatic ring substituent, such as dibenzylamine andN,N-di-4-methylbenzylamine; asymmetric secondary amines such asN-cyclohexyl-2-ethylhexylamine, N-cyclohexylbenzylamine,N-stearylbenzylamine and N-2-ethylhexylbenzylamine; alicyclic tertiaryamines such as N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine andtricyclohexylamine; tertiary amines having an aromatic ring substituent,such as tribenzylamine and tri-4-methylbenzylamine; amines having etherbonds such as morpholine, 3-methoxypropylamine, 3-ethoxypropylamine,3-butoxypropylamine, 3-decyloxypropylamine, and 3-lauryloxypropylamine;alkanolamines such as monoethanolamine, diethanolamine,monoisopropanolamine, monopropanolamine, butanolamine, triethanolamine,N,N-dimethylethanolamine, N-methylethanolamine, N-methyldiethanolamine,N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine,N-butylethanolamine, N-cyclohexyl-N-methylaminoethanol,N-benzyl-N-propylaminoethanol, or N-hydroxyethylpyrrolidine,N-hydroxyethylpiperazine, and N-hydroxyethylmorpholine; diamines such asethylenediamine, N-methylethylenediamine, N,N′-dimethylethylenediamine,N,N,N′,N′-tetramethylethylenediamine, 1,2-propanediamine,1,3-propanediamine, N,N-dimethyl-1,3-propanediamine,N-cyclohexyl-1,3-propanediamine, N-decyl-1,3-propanediamine, andN-isotridecyl-1,3-propanediamine; cyclic amines such asN,N-dimethylpiperazine, N-methoxyphenylpiperazine, N-methylpiperidine,N-ethylpiperidine, quinuclidine, diazabicyclo[2,2,2]octane, and1,8-diazabicyclo[5,4,0]-7-undecene; aromatic amines such as pyridine andquinoline; and the like; or mixtures thereof.

Among them, preferable examples include at least one selected fromprimary, secondary, or tertiary amines of straight or branched alkylhaving 4 to 20 carbon atoms, or alkanolamines, and specific examplesinclude butylamine, hexylamine, cyclohexylamine, octylamine,tridecylamine, stearylamine, dihexylamine, di-2-ethylhexylamine,straight or branched ditridecylamine, distearylamine, tributylamine,trioctylamine, straight or branched tritridecylamine, tristearylamine,N,N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, andmorpholine.

The mixed-coordination type heteropolyanion compound is more preferablyused in the form of a salt of at least one selected from these aminecompounds represented by the general formula (1) with at least oneselected from H₃PW_(x)Mo_(12-x)O₄₀.nH₂O (phosphotungstomolybdicacid.n-hydrate), H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O (phosphovanadomolybdicacid.n-hydrate), H₄SiW_(x)Mo_(12-x)O₄₀.nH₂O (silicotungstomolybdicacid.n-hydrate), and H_(4+x)SiV_(x)Mo_(12-x)O₄₀.nH₂O(silicovanadomolybdic acid.n-hydrate).

With respect to the mixed-coordination type heteropolyanion compound,mixed-coordination type heteropoly acids of H₃PW_(x)Mo_(12-x)O₄₀.nH₂O(phosphotungstomolybdic acid.n-hydrate), H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O(phosphovanadomolybdic acid.n-hydrate), and H₄SiW_(x)Mo_(12-x)O₄₀.nH₂O(silicotungstomolybdic acid.n-hydrate), or organic amine salts of thesemixed-coordination type heteropoly acids are most preferable.

The mixed-coordination type heteropolyanion compound is preferably addedin an amount of 0.01 to 10 parts by weight, and further preferably in anamount of 0.01 to 5 parts by weight, based on 100 parts by weight of themetallic particles.

The mixed-coordination type heteropolyanion compound for use in thepresent invention may be added at the time of pulverizing or extending araw material metal powder by a ball mill, may be mixed in a slurry inwhich a solvent is added to the metallic particles, or may be kneaded ina paste having a reduced amount of a solvent. The mixed-coordinationtype heteropolyanion compound may also be added to the metallicparticles as it is, or may also be diluted by a solvent and added. Inorder to achieve a uniformly mixed state, the mixed-coordination typeheteropolyanion compound is more preferably diluted by a solvent inadvance and added. Examples of the solvent used in dilution includewater, alcohols such as methanol, ethanol, propanol, butanol,isopropanol, and octanol; ether-alcohols and esters thereof, such asethylene glycol monoethyl ether, ethylene glycol monobutyl ether,diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,propylene glycol monoethyl ether, propylene glycol monomethyl ether, anddipropylene glycol monomethyl ether; and glycols such as ethyleneglycol, propylene glycol, 1,3-butanediol, 1,4-butanediol,polyoxyethylene glycol, polyoxypropylene glycol, and ethylene propyleneglycol. The solvent may be dissolved by an acid or alkali, and added.

A silicon-containing compound for use in the present invention isselected from compounds represented by the following general formula(2), (3), (4) or (5):

[Formula 14]

R4mSi(OR5)4-m  (2)

(wherein R4 is a hydrogen atom or a hydrocarbon group having 1 to 30carbon atoms that may optionally contain a halogen group, and R5 is ahydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R4 andR5 may be the same or different, wherein when the numbers of R4 and R5are each two or more, each of R4 and R5 may be the same, may bepartially the same, or may be all different; and 1≦m≦3.)

[Formula 15]

R6pR7qSi(OR8)4-p-q  (3)

(wherein R6 is a group containing a reactive group that can bechemically bound to other functional group, R7 is a hydrogen atom or ahydrocarbon group having 1 to 30 carbon atoms that may optionallycontain a halogen group, and R8 is a hydrogen atom or a hydrocarbongroup having 1 to 8 carbon atoms. When the numbers of R6, R7 and R8 areeach two or more, each of R6, R7 and R8 may be the same, may bepartially the same, or may be all different; and 1≦p≦3, 0≦q≦2, and1≦p+q≦3.)

[Formula 16]

Si(OR9)4  (4)

(wherein R9 is, each, a hydrogen atom or a hydrocarbon group having 1 to8 carbon atoms, wherein when the number of R9 is two or more, each of R9may be the same, may be partially the same, or may be all different.)

[Formula 17]

R10rSiCl4-r  (5)

(wherein R10 is a hydrogen atom or a hydrocarbon group having 1 to 30carbon atoms that may optionally contain a halogen group, wherein whenthe number of R10 is two or more, each of R10 may be the same, may bepartially the same, or may be all different; and 0≦r≦3.).

The hydrocarbon group in R4 of the formula (2) includes methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl,phenyl, benzyl and naphthyl, wherein these may be branched or straight,and may contain a halogen group such as fluorine, chlorine and bromine.Among them, a hydrocarbon group having 1 to 18 carbon atoms isparticularly preferable. When the number of R4 is two or more, R4 may beall the same, may be partially the same, or may be all different. Thenumber of R4 in the molecule, in the formula (2), preferably satisfiesthe following: m=1 to 3, and more preferably m=1 or 2.

The hydrocarbon group in R5 of the formula (2) includes methyl, ethyl,propyl, butyl, hexyl and octyl, wherein these may be branched orstraight. Among these hydrocarbon groups, methyl, ethyl, propyl andbutyl are particularly preferable. When the number of R5 is two or more,R5 may be all the same, may be partially the same, or may be alldifferent.

The silicon-containing compound in such a formula (2) includesmethyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane,trimethylmethoxysilane, trimethylethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-propyltributoxysilane, butyltrimethoxysilane,butyltriethoxysilane, butyltributoxysilane, dibutyldimethoxysilane,dibutyldiethoxysilane, dibutyldibutoxysilane, isobutyltrimethoxysilane,isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane,dihexyldimethoxysilane, dihexyldiethoxysilane, octyltrimethoxysilane,octyltriethoxysilane, dioctyldimethoxysilane, dioctyldiethoxysilane,dioctylethoxybutoxysilane, decyltrimethoxysilane, decyltriethoxysilane,didecyldimethoxysilane, didecyldiethoxysilane,octadecyltrimethoxysilane, octadecyltriethoxysilane,dioctadecyldimethoxysilane, dioctadecyldiethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane, trifluoropropyltrimethoxysilane,heptadecafluorodecyltrimethoxysilane,tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane,3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,3-chloropropyltributoxysilane, and the like.

The reactive group that can be chemically bound to other functionalgroup in R6 of the formula (3) includes a vinyl group, an epoxy group, astyryl group, a methacryloxy group, an acryloxy group, an amino group,an ureido group, a mercapto group, a polysulfide group, an isocyanategroup, and the like.

When the number of R6 is two or more, R6 may be all the same, may bepartially the same, or may be all different. The number of R6 in themolecule, in the formula (3), preferably satisfies the following: p=1 to3, and more preferably p=1.

The hydrocarbon group in R7 of the formula (3) includes methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl,phenyl, benzyl and naphthyl, wherein these may be branched or straight,and may contain a halogen group such as fluorine, chlorine and bromine.Among them, a hydrocarbon group having 1 to 18 carbon atoms isparticularly preferable. When the number of R7 is two or more, R7 may beall the same, may be partially the same, or may be all different.

The hydrocarbon group in R8 of the formula (3) includes methyl, ethyl,propyl, butyl, hexyl and octyl, wherein these may be branched orstraight. Among these hydrocarbon groups, methyl, ethyl, propyl andbutyl are particularly preferable. When the number of R8 is two or more,R8 may be all the same, may be partially the same, or may be alldifferent.

The silicon-containing compound in such a formula (3) includesvinyltrimethoxysilane, vinyltriethoxysilane,vinyl-tris(2-methoxyethoxy)silane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-glycidoxypropylmethyldiethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,N-methyl-3-aminopropyl-trimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane,N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane,3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl-triethoxysilane,bis(triethoxysilylpropyl)tetrasulfide,3-isocyanatepropyltriethoxysilane, and the like.

The hydrocarbon group in R9 of the formula (4) includes methyl, ethyl,propyl, butyl, hexyl, octyl, and the like, and these may be branched orstraight. Among these hydrocarbon groups, methyl, ethyl, propyl andbutyl are particularly preferable. Four R9 may be all the same, may bepartially the same, or may be all different.

The silicon-containing compound in such a formula (4) includestetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane,tetrabutoxysilane, and the like. Among them, tetraethoxysilane isparticularly preferable.

The hydrocarbon group in R10 of the formula (5) includes methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl,phenyl, benzyl, naphthyl, and the like, and these may be branched orstraight, and may contain a halogen group such as fluorine, chlorine andbromine. Among them, a hydrocarbon group having 1 to 12 carbon atoms isparticularly preferable. When the number of R10 is two or more, R10 maybe all the same, may be partially the same, or may be all different. Thenumber of R10 in the molecule, in the formula (5), preferably satisfiesthe following: r=0 to 3, and more preferably r=1 to 3.

The silicon-containing compound in such a formula (5) includesmethyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane,octyldimethylchlorosilane, phenyltrichlorosilane, vinyltrichlorosilane,tetrachlorosilane, and the like.

In each of the general formulas (2), (3), (4) and (5) of the presentinvention, one may be used, or two or more may be used in combination.

A hydrolysate of the silicon-containing compound and/or a condensationreaction product thereof is obtained by stirring and mixing thesilicon-containing compound and an amount of water required forperforming a hydrolysis reaction together with a hydrolysis catalyst. Inthat case, a hydrophilic solvent can also be used if necessary. The timefor the hydrolysis reaction is adjusted depending on the type of thesilicon-containing compound, the temperature at the time of hydrolysis,and the type and concentration of the hydrolysis catalyst.

Examples of the catalyst for the hydrolysis reaction of thesilicon-containing compound and/or the condensation reaction thereof,that can be used, include inorganic acids such as hydrochloric acid,nitric acid, sulfuric acid and phosphoric acid; organic acids such asbenzoic acid, acetic acid, chloroacetic acid, salicylic acid, oxalicacid, picric acid, phthalic acid and malonic acid; and phosphonic acidssuch as vinylphosphonic acid, 2-carboxyethanephosphonic acid,2-aminoethanephosphonic acid and octanephosphonic acid; and the like.These hydrolysis catalysts may be used solely or in combinations of twoor more thereof. Examples thereof also include inorganic alkalis such asammonia, sodium hydroxide and potassium hydroxide; inorganic alkalisalts such as ammonium carbonate, ammonium hydrogen carbonate, sodiumcarbonate and sodium hydrogen carbonate; amines such as monomethylamine,dimethylamine, trimethylamine, monoethylamine, diethylamine,triethylamine, monoethanolamine, diethanolamine, triethanolamine,N,N-dimethylethanolamine, ethylenediamine, pyridine, aniline, choline,tetramethylammonium hydroxide and guanidine; and salts of organic acid,such as ammonium formate, ammonium acetate, monomethylamine formate,dimethylamine acetate, pyridine lactate, guanidinoacetic acid andaniline acetate. These hydrolysis catalysts may be used singly or incombinations of two or more thereof.

As a raw material for the hydrolysis reaction of the silicon-containingcompound and/or the condensation reaction thereof, an oligomer which ispartially condensed in advance may be used.

The condensation reaction of the hydrolysate of the silicon-containingcompound may be performed at the same time with the hydrolysis reactionof the silicon-containing compound, or may be performed in a separatestep from the hydrolysis reaction, using a different catalyst ifnecessary. In that case, heating may be performed if necessary.

The hydrolysis reaction of the silicon-containing compound and/or thecondensation reaction may also be performed after or before adding thesilicon-containing compound to the metallic particles and themixed-coordination type heteropolyanion compound. The silicon-containingcompound does not need to be completely hydrolyzed.

The hydrolysis reaction of the silicon-containing compound and/or thecondensation reaction is preferably performed using a solvent. Examplesof the solvent for use in dilution include water; alcohols such asmethanol, ethanol, propanol, butanol, isopropanol and octanol;ether-alcohols and esters thereof, such as ethylene glycol monoethylether, ethylene glycol monobutyl ether, diethylene glycol monoethylether, diethylene glycol monobutyl ether, propylene glycol monoethylether, propylene glycol monomethyl ether and dipropylene glycolmonomethyl ether; and glycols such as ethylene glycol, propylene glycol,1,3-butanediol, 1,4-butanediol, polyoxyethylene glycol, polyoxypropyleneglycol and ethylenepropylene glycol. When alcohols or ether alcohols areused for the solvent, an exchange reaction of an alkoxy group in thesilicon-containing compound with the solvent may occur, but suchalcohols may be used for the hydrolysis reaction as they are.

The hydrolysate of the silicon-containing compound and/or the condensatethereof is preferably added in an amount of 0.01 to 50 parts by weight,and more preferably 1 to 30 parts by weight, based on 100 parts byweight of the metallic particles.

The hydrolysate of the silicon-containing compound and/or the condensatethereof, used in the present invention, may be added at the time ofpulverizing or extending a raw material metal powder by a ball mill, maybe mixed in a slurry in which the solvent is added to the metallicparticles, or may be kneaded in a paste having a reduced amount of thesolvent.

A predetermined amount to be added may be initially added at once, ormay be continuously added over a predetermined time. They may be addedbefore the mixed-coordination type heteropolyanion compound is added tothe metal particles, or may be added after being previously mixed withthe mixed-coordination type heteropolyanion compound, but are preferablyadded after the mixed-coordination type heteropolyanion compound isadded.

The present invention can further contain an organic oligomer or polymerin order to achieve a metallic pigment composition that is excellent inadhesion and chemical resistance when forming a coating film. Thepresent invention can also further contain at least one selected fromthe group consisting of (i) inorganic phosphoric acids or salts thereof;and (ii) acidic organic phosphoric or phosphorous acid esters or saltsthereof; in order to have excellent in storage stability when forming acoating film.

As the organic oligomer or polymer included in the present invention, anacrylic resin and/or a polyester resin is preferably used. The organicoligomer or polymer contained in the present invention preferably hasinteraction with at least one of the metallic particles, themixed-coordination type heteropolyanion compound, and the hydrolysate ofthe silicon-containing compound and/or the condensate thereof, whichcoexist. Therefore, the acrylic resin is preferably a polymer made ofmonomers which can interact with at least one of the metallic particles,the mixed-coordination type heteropolyanion compound, and thehydrolysate of the silicon-containing compound and/or the condensatethereof, which coexist, and at least one of monomers which can have acrosslinked structure, and in that case, any other monomers may beoptionally used in combination.

The monomers which can interact with at least one of the metallicparticles, the mixed-coordination type heteropolyanion compound, and thehydrolysate of the silicon-containing compound and/or the condensatethereof, which coexist, are preferably at least one selected from thegroup consisting of, for example, radical and/or ionic polymerizableunsaturated carboxylic acid; phosphoric acid or phosphonic acid esterhaving a radical and/or ionic polymerizable double bond; a compoundhaving a radical and/or ionic polymerizable double bond and anisocyanate group; a compound having a radical and/or ionic polymerizabledouble bond and an epoxy group; a compound having a radical and/or ionicpolymerizable double bond and an amino group; a compound having aradical and/or ionic polymerizable double bond and a hydrolyzable silylgroup; a compound having a radical and/or ionic polymerizable doublebond and a sulfone group; a compound having a radical and/or ionicpolymerizable double bond and a hydroxyl group; and the like.

Examples of the radical and/or ionic polymerizable unsaturatedcarboxylic acid include acrylic acid, methacrylic acid, itaconic acid,crotonic acid, citraconic acid, fumaric acid, maleic acid, maleicanhydride, monomethyl maleate, monoethyl maleate, monooctyl maleate,monomethyl fumarate, monoethyl fumarate, monooctyl fumarate,β-carboxyethyl(meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalicacid, 2-(meth)acryloyloxypropylhexahydrophthalic acid,2-methacroyloxyethylsuccinic acid, 2-methacroyloxyethylmaleic acid,2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxypropylphthalicacid, myristoleic acid, oleic acid, eicosadienoic acid, docosadienoicacid, and the like.

Among them, acrylic acid, methacrylic acid, itaconic acid, fumaric acid,maleic acid, maleic anhydride, and the like are preferably used.

As the phosphoric acid or phosphonic acid ester having a radical and/orionic polymerizable double bond, a mono or diester of phosphoric acid orphosphonic acid is used. Among them, a mono or diester of phosphoricacid is preferably used, and such a compound is represented by thefollowing general formula (8):

(wherein R17, R18 and R19 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, or a grouprepresented by the following general formula (9), wherein one or two ofR17, R18 and R19 are a hydrogen atom, one or two thereof are thefollowing general formula (9), and the total number of carbon atoms ofR17, R18 and R19 is 4 or more. m represents a numerical value of 0 or1.)

(wherein R20 and R23 represent a hydrogen atom or a methyl group, R21 isa trivalent organic group having 2 to 8 carbon atoms that may optionallycontain an oxygen atom, R22 represents a hydrogen atom or the followinggeneral formula (10). h represents a numerical value of 0 or 1 and irepresents a numerical value of 0 to 10.)

[Formula 20]

—CH²X  (10)

(wherein X represents a hydrogen atom or a chlorine atom.).

Specific examples thereof include 2-(meth)acryloyloxyethyl acidphosphate, di-2-(meth)acryloyloxyethyl acid phosphate,tri-2-(meth)acryloyloxyethyl phosphate and any mixtures thereof;2-(meth)acryloyloxypropyl acid phosphate, di-2-(meth)acryloyloxypropylacid phosphate, tri-2-(meth)acryloyloxypropyl phosphate and any mixturesthereof; phenyl-2-(meth)acryloyloxyethyl acid phosphate,butyl-2-(meth)acryloyloxyethyl acid phosphate,octyl-2-(meth)acryloyloxyethyl acid phosphate, bis(2-chloroethyl)vinylphosphonate, 3-chloro-2-acid phosphoxypropyl(meth)acrylate, acidphosphoxy-polyoxyethylene glycol mono(meth)acrylate and acidphosphoxy-polyoxypropylene glycol mono(meth)acrylate. These can also beoptionally used in the form of a salt with an inorganic base or anorganic amine. The organic amine used herein is represented by thefollowing general formula (6):

(wherein R11, R12 and R13 may be the same or different, are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R11 and R12 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, R11 and R12 are optionally taken together with a nitrogen atom toform a 5-membered or 6-membered ring that is capable of additionallycontaining a nitrogen or oxygen atom as a crosslinking member, or R11,R12 and R13 are optionally taken together to form a multi-memberedmultiring that is capable of containing one or more additional nitrogenatoms and/or oxygen atoms as a crosslinking members. R11, R12 and R13are not a hydrogen atom at the same time. n represents a numerical valueof 1 to 2.).

Among them, 2-(meth)acryloyloxyethyl acid phosphate,di-2-(meth)acryloyloxyethyl acid phosphate, tri-2-(meth)acryloyloxyethylphosphate and any mixtures thereof; 2-(meth)acryloyloxypropyl acidphosphate, di-2-(meth)acryloyloxypropyl acid phosphate,tri-2-(meth)acryloyloxypropyl phosphate and any mixtures thereof; andorganic amine salts thereof, and the like, in particular, salts such asethanolamine salts and morpholine salts are preferably used.

Examples of the compound having a radical and/or ionic polymerizabledouble bond and an isocyanate group include2-isocyanatoethyl(meth)acrylate, 2-isocyanatoethoxyethyl(meth)acrylate,1,1-bis(acryloyloxymethyl)ethyl isocyanate, methacryloyloxyphenylisocyanate, and the like, and these are preferably used.

Examples of the compound having a radical and/or ionic polymerizabledouble bond and an epoxy group include glycidyl(meth)acrylate,methylglycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate,epoxylated polybutadiene, and the like, and these are preferably used.

Examples of the compound having a radical and/or ionic polymerizabledouble bond and an amino group include aminoethyl(meth)acrylate,dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,morpholinoethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylamide,2-aminoethyl vinyl ether, 2-dimethylaminoethyl vinyl ether,N,N-dimethylaminopropyl(meth)acrylamide, amino styrene,N,N-dimethylaminostyrene, vinylbenzylamine, allylamine, and the like.

Among them, aminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,diethylaminoethyl(meth)acrylate, allylamine, and the like are preferablyused.

Examples of the compound having a radical and/or ionic polymerizabledouble bond and a hydrolyzable silyl group include(meth)acryloyloxypropyltrimethoxysilane,(meth)acryloyloxypropyltriethoxysilane,(meth)acryloyloxypropylmethyldimethoxysilane,(meth)acryloyloxypropylmethyldiethoxysilane,(meth)acryloyloxyethoxypropyltrimethoxysilane,(meth)acryloyloxymethyldimethylsilanol, vinyltrimethoxysilane,vinyltriethoxysilane, and the like.

Among them, (meth)acryloyloxypropyltrimethoxysilane,(meth)acryloyloxypropyltriethoxysilane, and the like are preferablyused.

Examples of the compound having a radical and/or ionic polymerizabledouble bond and a sulfone group include p-styrenesulfonic acid,allylsulfosuccinic acid, 3-sulfopropyl(meth)acrylate, and the like, andthese are preferably used.

Examples of the compound having a radical and/or ionic polymerizabledouble bond and a hydroxyl group include (meth)acrylic acid estershaving activated hydrogen, such as 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate,3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,2-hydroxy-3-chloropropyl(meth)acrylate,2-hydroxy-3-phenoxypropyl(meth)acrylate,(4-hydroxymethylcyclohexyl)(meth)acrylate,2-(meth)acryloyloxyethyl-2-hydroxyethylphthalate, polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(meth)acrylate,caprolactone modified hydroxyethyl(meth)acrylate, glycerolmono(meth)acrylate and trimethylolpropane mono(meth)acrylate;hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether,4-hydroxybutyl vinyl ether and hydroxycyclohexyl vinyl ether;unsaturated alcohols such asbutene-1-ol-3,2-methylbutene-3-ol-2,3-methylbutene-3-ol-1 and3-methylbutene-2-ol-1; N-methylol(meth)acrylamide; and the like.

Among them, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,and the like are preferably used.

These monomers which can interact with at least one of the metallicparticles, the mixed-coordination type heteropolyanion compound, thehydrolysate of the silicon-containing compound and/or the condensatethereof, which co-exist, may be used solely, or two or more thereof maybe mixed for use.

With respect to the amount used, the monomers are generally preferablyadded in an amount of 0.01 to 30 parts by weight, and further preferably0.1 to 20 parts by weight, based on 100 parts by weight of the metallicparticles.

As the monomers which can have a crosslinked structure, a monomer havingat least two radical and/or ionic polymerizable double bonds in onemolecule is preferable.

Examples of a monomer having two radical and/or ionic polymerizabledouble bonds in one molecule include ethyleneglycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,1,9-nonanediol di(meth)acrylate, 1,6-hexanediol diglycidyletherdi(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerindi(meth)acrylate, di(meth)acrylate of neopentyl glycol propyleneoxideadduct, diethylene glycol di(meth)acrylate, triethylene glycoldi(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, tripropylene glycol di(meth)acrylate,polypropylene glycol di(meth)acrylate, polytetramethylene glycoldi(meth)acrylate, hydroxypivalic acid neopentyl glycol esterdi(meth)acrylate, di(meth)acrylate of bisphenol A ethyleneoxide adduct,di(meth)acrylate of hydrogenated bisphenol A propyleneoxide adduct,dimethylol tricyclodecane di(meth)acrylate, glycerin methacrylateacrylate, divinylbenzene, vinyl adipate, vinyl(meth)acrylate, vinylcrotonate, vinyl cinnamate, allyl vinyl ether, isopropenyl vinyl ether,and the like.

Examples of a monomer having three or more radical and/or ionicpolymerizable double bonds in one molecule include trimethylolpropanetri(meth)acrylate, tri(meth)acrylate of glycerin ethylene oxide adduct,tri(meth)acrylate of trimethylolpropane propylene oxide adduct,ditrimethylolpropane tetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, hexa(meth)acrylate ofdipentaerythritol caprolactone adduct, dipentaerythritoltri(meth)acrylate tripropionate, dipentaerythritol hexa(meth)acrylatemonopropionate, and the like. These monomers which can have acrosslinked structure may be used solely, or two ore more thereof may bemixed for use.

With respect to the amount used, the monomers are generally preferablyadded in an amount of 0.01 to 50 parts by weight, and further preferably1 to 30 parts by weight, based on 100 parts by weight of the metallicparticles.

In addition to the monomers which can interact with at least one of themetallic particles, the mixed-coordination type heteropolyanioncompound, and the hydrolysate of the silicon-containing compound and/orthe condensate thereof, which coexist, and the monomers which can have acrosslinked structure, other monomers can also be copolymerized.

Examples of other monomers which can also be copolymerized include(meth)acrylic acid esters such as methyl(meth)acrylate,ethyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate,hexyl(meth)acrylate, cyclohexyl(meth)acrylate,2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, benzyl(meth)acrylate,isobornyl(meth)acrylate, dicyclopentenyl(meth)acrylate andfurfuryl(meth)acrylate; (meth)acrylic acid esters having afluorine-containing side chain such as trifluoroethyl(meth)acrylate,2,2,3,3-tetrafluoropropyl(meth)acrylate andperfluorooctylethyl(meth)acrylate; unsaturated amides such as(meth)acrylamide, N,N-dimethyl(meth)acrylamide,N-isopropyl(meth)acrylamide, (meth)acryloyl morpholine and diacetone(meth)acrylamide; vinyl esters such as vinyl acetate, vinyl propionate,vinyl pivalate, vinyl caprate, vinyl stearate and vinyl benzoate; vinylethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether,cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether and lauryl vinyl ether;fluorinated olefins such as tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene and perfluoropentene-1;styrene, α-methylstyrene, vinyltoluene, (meth)acrylonitrile, dibutylfumarate, and the like.

Furthermore, monomers having a condensed polycyclic hydrocarbonskeleton, such as pentalene, indene, naphthalene, azulene, heptalene,biphenylene, indacene, fluorene, 9,9-bisphenylfluorene, phenanthrene,anthracene, triphenylene, pyrene and perylene, and monomers having acondensed heterocyclic skeleton, such as indole, quinoline, indolizine,carbazole, acridine and phenoxazine can also be used. Specific examplesthereof include vinylnaphthalene, divinylnaphthalene, vinylanthracene,divinylanthracene, N-vinylcarbazole, N-acryloylcarbazole,divinylfluorene, 9,9-bis[4-((meth)acryloyloxyethoxy)phenyl]fluorene and9,9-bis[4-((meth)acryloyloxy-2(or 1)methylethoxy)phenyl]fluorene.

All the above monomers may be used solely, or two or more thereof may bemixed for use.

The amount used is, for example, generally in the order of 0 to 30 partsby weight based on 100 parts by weight of the metallic particles.

These (meth)acrylic monomers are polymerized by any known method such asradical polymerization and ionic polymerization, and usually simplypolymerized by a radical polymerization method using a polymerizationinitiator.

Examples of the radical polymerization initiator include peroxides suchas benzoyl peroxide, lauroyl peroxide andbis-(4-t-butylcyclohexyl)peroxydicarbonate; azo compounds such as2,2′-azobis-isobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile;and the like.

The amount used is not particularly limited, and usually in the order of0.1 to 20 parts by weight based on 100 parts by weight of a monomerhaving a radical polymerizable double bond.

Polymerization is performed in a slurry, in which the solvent is addedto the metallic particles, by adding the monomer and the polymerizationinitiator simultaneously or separately at once, simultaneously orseparately in portions, or simultaneously or separately in series.

In particular, a method of adding the monomer and the polymerizationinitiator separately in portions or in series is preferably used.

The monomer and the polymerization initiator may be added at the sametime as adding the mixed-coordination type heteropolyanion compound andthe hydrolysate of the silicon-containing compound and/or the condensatethereof to the metallic particles, but may be preferably added in adifferent kind of solvent if necessary, after adding themixed-coordination type heteropolyanion compound and the hydrolysate ofthe silicon-containing compound and/or the condensate thereof, therebyperforming polymerization.

The solvent at the time of adding and polymerization reaction may be ahydrophobic solvent or a hydrophilic solvent. Examples of thehydrophobic solvent include mineral spirit, solvent naphtha, LAWS (LowAromatic White Spirit), HAWS (High Aromatic White Spirit), toluene,xylene, esters such as ethyl acetate and butyl acetate, and ketones suchas methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.Examples of the hydrophilic solvent that can be used include alcoholssuch as methanol, ethanol, propanol, butanol, isopropanol and octanol,ether alcohols and esters thereof, such as ethylene glycol monoethylether, ethylene glycol monobutyl ether, diethylene glycol monoethylether, diethylene glycol monobutyl ether, propylene glycol monoethylether, propylene glycol monomethyl ether and dipropylene glycolmonomethyl ether, glycols such as propylene glycol, polyoxyethyleneglycol, polyoxypropylene glycol and ethylene propylene glycol, and thelike. These can be used solely or used as a mixture thereof.

Solvents having a relatively low polarity, for example, mineral spirit,solvent naphtha, LAWS, HAWS, toluene, xylene, butyl acetate, methylisobutyl ketone, cyclohexanone, octanol, ether alcohols and estersthereof, such as ethylene glycol monoethyl ether, ethylene glycolmonobutyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, propylene glycol monoethyl ether, propylene glycolmonomethyl ether and dipropylene glycol monomethyl ether, and the likeare more preferably exemplified.

The polymerization reaction in the slurry is performed with theconcentration of the metallic particles in the slurry being preferably 5to 20% by weight. The polymerization temperature and time areappropriately determined depending on the progression of the reaction,and usually the temperature is about 0° C. to 150° C. and the time isabout 0.5 to 48 hours.

Examples of the polyester resins include polyester resins obtained by acondensation reaction of one or a mixture selected from the group ofcarboxylic acids such as succinic acid, adipic acid, sebacic acid, dimeracid, maleic anhydride, phthalic anhydride, isophthalic acid,terephthalic acid, trimellitic acid and pyromellitic acid, with one or amixture of polyhydric alcohols selected from the group of the following:diols such as ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, tripropylene glycol,1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol,1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol,2,5-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-hexanediol,1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol,2-butyl-2-ethyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol; triolssuch as glycerin and trimethylolpropane; and tetraols such asdiglycerin, dimethylolpropane and pentaerythritol.

With respect to the amount used, the polyester resin is generally andpreferably added in an amount of 0.01 to 50 parts by weight, and furtherpreferably 1 to 30 parts by weight based on 100 parts by weight of themetallic particles.

The organic oligomer or polymer for use in the present invention may beobtained by starting polycondensation at the same time as or afteradding the mixed-coordination type heteropolyanion compound and thehydrolysate of the silicon-containing compound and/or the condensatethereof to the metallic particles, or may be added in advance in thestate of oligomer or polymer, but is preferably obtained by performingpolycondensation.

Examples of the inorganic phosphoric acids for use in the presentinvention include orthophosphoric acid, pyrophosphoric acid,metaphosphoric acid, triphosphoric acid, tetraphosphoric acid,phosphorous acid, polyphosphoric acid, laurylphosphoric acid,polyoxypropylene oleylether phosphoric acid and dipolyoxyethylenenonylphenylether phosphoric acid. Among them, orthophosphoric acid,pyrophosphoric acid, metaphosphoric acid, triphosphoric acid,tetraphosphoric acid and phosphorous acid are particularly preferable.

The acidic organic phosphoric acid esters or acidic organic phosphorousacid esters (in the present application, referred to also as “acidicorganic phosphoric or phosphorous acid esters”) for use in the presentinvention are represented by the following general formula (7) or (8):

(wherein R14, R15 and R16 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, or a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, wherein oneor two of R14, R15 and R16 are a hydrogen atom and the total number ofcarbon atoms of R14, R15 and R16 is 4 or more. m represents a numericalvalue of 0 or 1.)

(wherein R17, R18 and R19 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, or a grouprepresented by the following general formula (9), wherein one or two ofR17, R18 and R19 are a hydrogen atom, one or two thereof are thefollowing general formula (9), and the total number of carbon atoms ofR17, R18 and R19 is 4 or more. m represents a numerical value of 0 or1.)

(wherein R20 and R23 represent a hydrogen atom or a methyl group, R21 isa trivalent organic group having 2 to 8 carbon atoms that may optionallycontain an oxygen atom, and R22 represents a hydrogen atom or thefollowing general formula (10). h represents a numerical value of 0 or 1and i represents a numerical value of 0 to 10.)

[Formula 25]

—CH²X  (10)

(wherein X represents a hydrogen atom or a chlorine atom.).

Examples of the general formula (7) include respective monoesters anddiesters, such as methyl acid phosphate, ethyl acid phosphate, butylacid phosphate, octyl acid phosphate, lauryl acid phosphate, tridecylacid phosphate, stearyl acid phosphate, oleyl acid phosphate, tetracosylacid phosphate, nonylphenyl acid phosphate, phenyl acid phosphate,polyoxyethylene alkyl ether acid phosphate, polyoxyethylene alkyl phenylether acid phosphate, acid phosphooxyethyl methacrylate, acidphosphooxypolyoxyethylene glycol monomethacrylate, acidphosphooxypolyoxypropylene glycol monomethacrylate, 3-chloro-2-acidphosphooxypropyl methacrylate, diethyl hydrogen phosphite, dilaurylhydrogen phosphite, dioleyl hydrogen phosphite and diphenyl hydrogenphosphite, and mixtures thereof. These acidic organic phosphoric orphosphorous acid esters may also partially include triesters of anunsubstituted inorganic phosphoric acid and/or triesters not exhibitingacidity. Among them, particularly preferable examples include monoestersand diesters, such as octyl acid phosphate, lauryl acid phosphate,tridecyl acid phosphate, stearyl acid phosphate, acidphosphooxypolyoxypropylene glycol monomethacrylate and dilauryl hydrogenphosphites, and mixtures thereof.

Examples of the general formula (8) include 2-(meth)acryloyloxyethylacid phosphate, di-2-(meth)acryloyloxyethyl acid phosphate andtri-2-(meth)acryloyloxyethyl phosphate, and any mixtures thereof;2-(meth)acryloyloxypropyl acid phosphate, di-2-(meth)acryloyloxypropylacid phosphate and tri-2-(meth)acryloyloxypropyl phosphate, and anymixtures thereof; phenyl-2-(meth)acryloyloxyethyl acid phosphate,butyl-2-(meth)acryloyloxyethyl acid phosphate,octyl-2-(meth)acryloyloxyethyl acid phosphate, bis(2-chloroethyl)vinylphosphonate, 3-chloro-2-acid phosphooxypropyl(meth)acrylate, acidphosphooxy-polyoxyethylene glycol mono(meth)acrylate and, acidphosphooxy-polyoxypropylene glycol mono(meth)acrylate, and the like.

Substances constituting the inorganic phosphoric acid salts or acidicorganic phosphoric or phosphorous acid ester salts for use in thepresent invention include alkali metals such as potassium and sodium,alkaline earth metals such as calcium and magnesium, ammonia, and aminesrepresented by the following general formula (6):

(wherein R11, R12 and R13 may be the same or different, are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, wherein R11 and R12are optionally taken together to form a 5-membered or 6-memberedcycloalkyl group, R11 and R12 are optionally taken together with anitrogen atom to form a 5-membered or 6-membered ring that is capable ofadditionally containing a nitrogen or oxygen atom as a crosslinkingmember, or R11, R12 and R13 are optionally taken together to form amulti-membered multiring that is capable of containing one or moreadditional nitrogen atoms and/or oxygen atoms as a crosslinking member.R11, R12 and R13 are not a hydrogen atom at the same time. n representsa numerical value of 1 to 2.).

Particularly preferable examples among these amines includediethylamine, triethylamine, propylamine, dipropylamine, tripropylamine,octylamine, dioctylamine and trioctylamine, and additionally primary,secondary and tertiary amines having a straight or branched alkyl grouphaving in the order of 10 to 20 carbon atoms, morpholine,N-methylmorpholine, ethanolamine, diethanolamine, N-methylethanolamine,N-methyldiethanolamine, N,N-dimethylethanolamine and triethanolamine.

(i) The inorganic phosphoric acids or salts thereof or (ii) acidicorganic phosphoric or phosphorous acid esters or salts thereof for usein the present invention may be added when the raw material metal powderis pulverized by a ball mill, may be mixed in a slurry in which thesolvent is added to the metallic pigment, or may be kneaded in a pastehaving a reduced amount of the solvent. In order to achieve a uniformlymixed state, they are preferably diluted with a solvent, mineral oil orthe like in advance and added. Examples of the solvent for use indilution include alcohols such as methanol and isopropanol, cellosolvessuch as propylene glycol monomethyl ether, hydrocarbon solvents such ashexane, octane, isooctane, benzene, toluene, xylene, tetralin anddecalin, industrial gasolines such as mineral spirit and solventnaphtha, esters such as ethyl acetate and butyl acetate, ketones such asmethyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, mineraloils, and the like.

In the production of the metallic pigment composition of the presentinvention, the order of the mixing of the mixed-coordination typeheteropolyanion compound, the hydrolysate of the silicon-containingcompound and/or the condensate thereof, and further at least oneselected from the group consisting of the organic oligomer or polymer,the inorganic phosphoric acids or salts thereof, and the acidic organicphosphoric or phosphorous acid esters or salts thereof, with themetallic particles; the polymerization of the organic oligomer orpolymer; or the hydrolysis and condensation reaction treatment of thesilicon-containing compound may be freely determined. However, it ispreferable to perform these operations in the presence of the solventselected from the examples described in items each describing eachcompound, and further, it is preferable to first perform the mixingtreatment or the hydrolysis and condensation reaction treatment of themixed-coordination type heteropolyanion compound and the hydrolysate ofthe silicon-containing compound and/or the condensate thereof inseparate steps or in a single step. In that case, it is more preferableto perform, after the mixing treatment with the mixed-coordination typeheteropolyanion compound, the mixing treatment or the hydrolysis andcondensation reaction treatment with the hydrolysate of thesilicon-containing compound and/or the condensate thereof.

Furthermore, it is preferable to perform, after treating themixed-coordination type heteropolyanion compound and the hydrolysate ofthe silicon-containing compound and/or the condensate thereof inseparate steps or in a single step, the mixing or polymerizationtreatment of at least one selected from the organic oligomer or polymer;the inorganic phosphoric acids or salts thereof; and the acidic organicphosphoric or phosphorous acid esters or salts thereof. When the organicoligomer or polymer and the inorganic phosphoric acids or salts thereofor acidic organic phosphoric or phosphorous acid esters or salts thereofare used together, they may be subjected to the mixing (polymerization)treatment in separate steps or in a single step, but, more preferably,the organic oligomer or polymer are subjected to the mixing orpolymerization treatment and thereafter the inorganic phosphoric acidsor salts thereof or the acidic organic phosphoric or phosphorous acidesters or salts thereof are subjected to the mixing treatment.

To the metallic pigment composition of the invention of the presentapplication may be further added at least one selected from anantioxidant, a light stabilizer, a polymerization inhibitor and asurfactant, in addition to the mixed-coordination type heteropolyanioncompound, the hydrolysate of the silicon-containing compound and/or thecondensate thereof, the organic oligomer or polymer, and/or theinorganic or organic phosphoric acid compound.

The antioxidant is typified by a phenol compound, a phosphorus compoundand a sulfur compound. As a suitable compound, exemplified are phenolcompounds such as 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol,2,6-di-t-butyl-p-cresol (BHT), 2,6-di-t-butyl-4-ethyl-phenol,2,4,6-tri-t-butylphenol, butylhydroxyanisole (BHA), 2,2′-methylenebis(4-methyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol),octadecyl-3-(3,5-di-t-butylphenyl)propionate (IRGANOX 1076),hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (IRGANOX259), thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](IRGANOX 1035), tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate(IRGANOX 3114),tetrakis[methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate]methane(IRGANOX 1010), calciumdiethylbis[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate](IRGANOX 1425 WL),ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate](IRGANOX 245), benzene propanoic acid,3,5-bis(1,1-dimethylethyl)-4-hydroxyalkylester (IRGANOX 1135),N,N′-hexane-1,6-diyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide](IRGANOX 1098) and tocopherol; phosphorus compounds such astriphenylphosphite, diphenylnonylphenylphosphite,tris-(2,4-di-t-butylphenyl)phosphite, trisnonylphenylphosphite,tris-(mono- and di-mixed nonylphenyl)phosphite,diphenylisooctylphosphite,2,2′-methylenebis(4,6-di-t-butylphenyl)octylphosphite,diphenylisodecylphosphite, phenyldiisodecylphosphite,diphenylmono(tridecyl)phosphite,2,2′-ethylidenebis(4,6-di-t-butylphenol)fluorophosphite,phenyldiisodecylphosphite, phenyldi(tridecyl)phosphite,tris(2-ethylhexyl)phosphite, tris(isodecyl)phosphite,tris(tridecyl)phosphite, dibutyl hydrogen phosphite,trilauryltrithiophosphite,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenediphosphonite,4,4′-isopropylidenediphenolalkyl(C12 to C15)phosphite,4,4′-butylidenebis(3-methyl-6-t-butylphenyl)di-tridecylphosphite,distearyl-pentaerythritoldiphosphite,bis(nonylphenyl)pentaerythritoldiphosphite,bis(2,4-di-t-butylphenyl)pentaerythritoldiphosphite, cyclic neopentanetetrayl bis(2,4-di-t-butylphenylphosphite), phenyl-bisphenol Apentaerythritoldiphosphite, tetraphenyl dipropylene glycol diphosphite,1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane,tetraphenyl tetra(tridecyl)pentaerythritol tetraphosphite, zincdialkyldithiophosphate (ZnDTP),3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide,3,5-di-t-butyl-4-hydroxybenzylphosphite-diethylester and a hydrogenatedbisphenol A phosphite polymer; sulfur compounds such asdilauryl-3,3′-thiodipropionic acid ester (DLTTDP),ditridecyl-3,3′-thiodipropionic acid ester,dimyristyl-3,3′-thiodipropionic acid ester (DMTDP),distearyl-3,3′-thiodipropionic acid ester (DSTDP),laurylstearyl-3,3′-thiodipropionic acid ester, pentaerythritoltetra(β-lauryl-thiopropionate)ester, stearylthiopropionamide,bis[2-methyl-4-(3-n-alkyl(C12 toC14)thiopropionyloxy)-5-t-butylphenyl]sulfide, dioctadecyldisulfide,2-mercaptonbenzimidazole, 2-mercapto-6-methylbenzimidazole and1,1′-thiobis(2-naphthol); ascorbic acid; and the like.

The light stabilizer is typified by a benzotriazole compound, abenzophenone compound, a salicylate compound, cyanoacrylate, an oxalicacid derivative, a hindered amine compound (HALS) and a hindered phenolcompound, some of which is used as the above-described antioxidant.

Examples of a suitable compound include benzotriazole compounds such as2-(2′-hydroxy-5′-methylphenyl)benzotriazole,3″,4″,2-(T-hydroxy-5′-t-octylphenyl)benzotriazole,2-(T-hydroxy-4′-t-octoxyphenyl)benzotriazole,2-(T-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-t-amylphenyl)benzotriazole,2-(T-hydroxy-3′-dodecyl-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-bis(α,α-dimethylbenzyl)phenylbenzotriazole,2-[2′-hydroxy-3′-(3″,4″,5″,6″-tetraphthalimidemethyl)-5′-methylphenyl]benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)-5-chlorobenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol,and a condensate ofmethyl-3-[3-t-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenylpropionateand polyethylene glycol (molecular weight: about 300); benzophenonecompounds such as 2,4-dihydroxybenzophenone,2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone,2-hydroxy-4-methoxy-2′-carboxybenzophenone,2-hydroxy-4-methoxy-5-sulfoxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone,bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, a polymer of4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone, and a mixture of2,2′-dihydroxy-4,4′-dimethoxybenzophenone and other tetrasubstitutedbenzophenone; salicylate compounds such as phenylsalicylate,2,5-di-t-butyl-4-hydroxybenzoic acid-n-hexadecylester,4-t-butylphenylsalicylate, 4-t-octylphenylsalicylate and2,4-di-t-butylphenyl-3′,5′-di-t-butyl-4′-hydroxybenzoate; cyanoacrylatecompounds such as ethyl(β,β-diphenyl)cyanoacrylate and2-ethylhexyl(β,β-diphenyl)cyanoacrylate; oxalic acid derivatives such as2-ethoxy-2′-ethyloxalic acid bisanilide,2-ethoxy-5-t-butyl-2′-ethyloxalic acid bisanilide and an oxalic acidanilide derivative; hindered amine (HALS) compounds such as[4-(4-hydroxy-3,5-di-t-butylphenyl)propionyl]-N-(4-hydroxy-3,5-di-t-butylphenyl)methyl-2,2,6,6-tetramethylpiperidine,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazineone),bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate,methyl-(N-methyl-2,2,6,6-tetramethyl-piperidinyl)sebacate,bis-(N-methyl-2,2,6,6-tetramethyl-piperidinyl)sebacate, decane diacidbis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester,bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate,a condensate of 1,2,3,4-butanecarboxylic acid,2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, a condensate of1,2,3,4-butanecarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol andtridecyl alcohol,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,poly[[6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine-2,4-diyl],[(2,2,6,6-tetramethylpiperidine)imino]hexamethylene[(2,2,6,6-tetramethylpiperidylimino]],poly[6-morpholino-s-triazine-2,4-diyl-2,2,6,6-tetramethylpiperidylimino-hexamethylene][2,2,6,6-tetramethylpiperidylimino]],a condensate of 1,2,3,4-butanetetracarboxylic acid,2,2,6,6-tetramethyl-4-piperidinol andβ,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol;and semicarbazide compounds such as 1,6-hexamethylenebis(N,N-dimethylsemicarbazide) and1,1,1′,1′-tetramethyl-4,4′-(methylene-di-p-phenylene)disemicarbazide.

The polymerization inhibitor is typified by phenols, quinones, a nitrocompound, a nitroso compound, amines and sulfides. Examples of asuitable compound include phenols such as hydroquinone,hydroquinonemonomethylether, mono-tert-butylhydroquinone, catechol,p-tert-butylcatechol, p-methoxyphenol, p-tert-butylcatechol,2,6-di-tert-butyl-m-cresol, pyrogallol, β-naphthol and4-methoxy-1-naphthol; quinones such as benzoquinone,2,5-diphenyl-p-benzoquinone, p-toluquinone and p-xyloquinone; nitrocompounds or nitroso compounds such as nitromethane, nitroethane,nitrobutane, nitrobenzene, a nitrobenzenesulfonic acid compound,m-dinitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-tert-butylnitroneand 5,5-dimethyl-1-pyrroline-1-oxide; amines such as chloranil-amine,diphenylamine, diphenylpicrylhydrazine, phenol-α-naphthylamine, pyridineand phenothiazine; and sulfides such as dithiobenzoylsulfide anddibenzyltetrasulfide.

Examples of the surfactant include non-ionic surfactants typified by:polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether,polyoxyethylene cetyl ether, polyoxyethylene stearyl ether andpolyoxyethylene oleyl ether; polyoxyalkylene alkylphenyl ethers such aspolyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether;polyoxyalkylene alkylaminoethers such as polyoxyethylenelaurylaminoether and polyoxyethylene stearylaminoether; sorbitan fattyacid esters such as sorbitan monolaurate, sorbitan monopalmitate,sorbitan monostearate and sorbitan monooleate; polyoxyalkylene sorbitanfatty acid esters such as polyoxyethylene sorbitan monolaurate,polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitanmonostearate and polyoxyethylene sorbitan monooleate; polyalkyleneglycol fatty acid esters such as polyethylene glycol monolaurate,polyethylene glycol monooleate, polyethylene glycol monostearate,polyethylene glycol dilaurate and polyethylene glycol distearate; andglycerin fatty acid esters such as lauric acid monoglyceride, stearicacid monoglyceride and oleic acid monoglyceride. Also, examples of thesurfactant include anionic surfactants typified by: sulfuric acid estersalts such as polyoxyethylene lauryl ether sulfate sodium,polyoxyethylene octyl phenyl ether sulfate sodium, polyoxyethylene nonylphenyl ether sulfate sodium, laurylsulfuric acid triethanolamine, sodiumlauryl sulfate, potassium lauryl sulfate and ammonium lauryl sulfate;sulfonic acid salts such as sodium dodecylbenzenesulfonate, sodiumalkylnaphthalenesulfonate and sodium dialkylsulfosuccinate; andphosphoric acid ester salts such as potassium alkylphosphate. Also,examples of the surfactant include cationic surfactants typified by:quaternary ammonium salts such as lauryl trimethyl ammonium chloride,cetyl trimethyl ammonium chloride and stearyl trimethyl ammoniumchloride. And, one, or two or more selected from the above examples canbe used as the surfactant. Among them, polyoxyethylene lauryl ether,polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,polyoxyethylene oleyl ether or a mixture thereof is particularlypreferably exemplified.

The metallic pigment composition obtained by the present invention canalso be used for organic solvent coatings, inks and the like.Additionally, the metallic pigment composition obtained by the presentinvention can be added to water-based coatings or water-based inks, inwhich resins as a coating film-forming component are dissolved ordispersed in a medium mainly containing water, thereby forming metallicwater-based coatings or metallic water-based inks. The metallic pigmentcomposition can also be kneaded with resins or the like and thus used asa waterproof binder or filler. The antioxidant, light stabilizer,polymerization inhibitor and surfactant may be added when the metallicpigment composition is blended in, for example, water-based coatings orwater-based inks, or resins.

When the metallic pigment composition obtained by the present inventionis used for coatings or inks, it may be added to (water-based) coatingsor (water-based) inks as it is, but is preferably added thereto afterbeing dispersed in a solvent in advance. The solvent here used includeswater, texanol, diethylene glycol monobutyl ether, propylene glycolmonomethyl ether and the like. Examples of the resins include acrylicresins, polyester resins, polyether resins, epoxy resins, fluorineresins and rosin resins.

Examples of the acrylic resins include (meth)acrylates such asmethyl(meth)acrylate, ethyl(meth)acrylate, isopropyl(meth)acrylate,n-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate andlauryl(meth)acrylate; (meth)acrylates having active hydrogen, such as2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,2-hydroxybutyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate and4-hydroxybutyl(meth)acrylate; unsaturated carboxylic acids such asacrylic acid, methacrylic acid, maleic acid and itaconic acid;unsaturated amides such as acrylamide, N-methylolacrylamide anddiacetoneacrylamide; and acrylic resins obtained by polymerizing one ora mixture selected from other polymerizable monomers such as glycidylmethacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile,dibutyl fumarate, p-styrenesulfonic acid and allylsulfosuccinic acid.

A polymerization method is generally emulsion polymerization, but theacrylic resins can also be produced by suspension polymerization,dispersion polymerization or solution polymerization. The emulsionpolymerization can also be stepwise polymerization.

Examples of the polyester resins include polyester resins obtained bycondensation reaction of one or a mixture selected from the group ofcarboxylic acids such as succinic acid, adipic acid, sebacic acid, dimeracid, maleic anhydride, phthalic anhydride, isophthalic acid,terephthalic acid, trimellitic acid and pyromellitic acid, with one or amixture of polyhydric alcohols selected from the group of diols such asethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol,1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol,2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol,2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol,2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol,2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol and2,2-diethyl-1,3-propanediol, triols such as glycerin andtrimethylolpropane, and tetraols such as diglycerin, dimethylolpropaneand pentaerythritol; and polycaprolactones obtained by ring-openingpolymerization of ε-caprolactone to a hydroxyl group of a low molecularweight polyol.

The polyether resins include polyether polyols obtained by adding one ora mixture of alkylene oxides such as ethylene oxide, propylene oxide,butylene oxide, cyclohexene oxide and styrene oxide to one or a mixtureof polyhydric hydroxyl compounds by means of a strong basic catalystsuch as hydroxide of lithium, sodium, potassium or the like, alcoholateor alkylamine; polyether polyols obtained by reacting alkylene oxidewith a polyfunctional compound such as ethylenediamines; polyetherpolyols obtained by ring-opening polymerization of cyclic ethers such astetrahydrofuran; so-called polymer polyols obtained by polymerizingacrylamide or the like by using these polyethers as a medium; and thelike.

These resins are preferably emulsified, dispersed or dissolved in water.Thus, carboxyl groups, sulfone groups and the like contained in theresins can be neutralized.

As a neutralizer for neutralizing the carboxyl groups, the sulfonegroups and the like, at least one selected from, for example, ammonia,and water-soluble amino compounds such as monoethanolamine, ethylamine,dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine,isopropylamine, diisopropylamine, triethanolamine, butylamine,dibutylamine, 2-ethylhexylamine, ethylenediamine, propylenediamine,methylethanolamine, dimethylethanolamine, diethylethanolamine andmorpholine can be used. Preferably, triethylamine anddimethylethanolamine which are tertiary amines, and the like can beused.

Preferable resins are acrylic resins and polyester resins.

A melamine curing agent, an isocyanate curing agent, and a resin such asurethane dispersion can be used in combination, if necessary.Furthermore, an inorganic pigment, an organic pigment, an extenderpigment, a silane coupling agent, a titanium coupling agent, adispersant, an antisettling agent, a leveling agent, a thickening agent,and a defoamer, which are generally added to coatings, can be combined.The surfactant may be further added in order to make dispersibility incoatings better. Also, the antioxidant, the light stabilizer and thepolymerization inhibitor may be further added in order to make storagestability of coatings better.

EXAMPLES

Hereinafter, Examples of the present invention will be illustrated.

Example 1

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) was added 465 g ofethylene glycol monobutyl ether and dispersed therein to form a slurry,and a solution of 1.0 g of a hydrate of phosphotungstomolybdic acid(H₃PW₆Mo₆O₄₀) in 30 g of ethylene glycol monobutyl ether was graduallyadded while stirring the slurry, and the resultant was stirred for 2hours while maintaining the slurry temperature at 70° C. Thereafter,10.0 g of tetraethoxysilane was further added, then 3.2 g of 25% ammoniawater and 5.2 g of distilled water were added thereto, and the resultantwas stirred for 2 hours. Thereafter, the resultant was heated to atemperature of 140° C. and stirred for 4 hours. After the completion ofthe reaction, the obtained slurry was filtered after cooling, therebyobtaining an aluminum pigment composition having a nonvolatile contentof 60%. The obtained aluminum pigment composition was dissolved in 1mol/L hydrochloric acid, the content of each element was measured by ICPemission spectroscopy, and as a result, it was found that the content ofW was 0.31 parts by weight, the content of Mo was 0.16 parts by weight,and the content of Si was 1.01 parts by weight, based on 100 parts byweight of Al.

Example 2

A tridecyl acid phosphate morpholine salt (3.0 parts by weight) wasadded based on 100 parts by weight of an aluminum metal component in thealuminum pigment composition obtained in Example 1, and the resultantwas kneaded at 40° C. for 2 hours to obtain an aluminum pigmentcomposition.

Example 3

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) was added 465 g ofpropylene glycol monomethyl ether acetate and dispersed therein to forma slurry, and a solution of 2.0 g of a hydrate of silicotungstomolybdicacid (H₄SiW₃Mo₉O₄₀) in 30 g of propylene glycol monomethyl ether wasgradually added while stirring the slurry, and the resultant was stirredfor 2 hours while maintaining the slurry temperature at 40° C.Thereafter, 10.0 g of tetraethoxysilane was added, then 3.2 g of 25%ammonia water and 5.2 g of distilled water were added, and the resultantwas further stirred for 2 hours. Thereafter, 5.0 g oftrifluoropropyltrimethoxysilane was added in the state of beingpreviously hydrolyzed by an aqueous 1 mol/L acetic acid solution and theresultant was heated to a temperature of 130° C., and the resultant wasstirred for 12 hours. After the completion of the reaction, the obtainedslurry was filtered after cooling, thereby obtaining an aluminum pigmentcomposition having a nonvolatile content of 55%. Furthermore, 0.5 partsby weight of 2,6-di-t-butyl-p-cresol was added based on 100 parts byweight of an aluminum metal component in the aluminum pigmentcomposition, and the resultant was kneaded. The obtained aluminumpigment composition was subjected to aging at 50° C. for 1 week. Thecontent of each element in this aluminum pigment composition wasmeasured in the same manner as Example 1, and it was found that thecontent of W was 0.34 parts by weight, the content of Mo was 0.53 partsby weight, and the content of Si was 1.50 parts by weight, based on 100parts by weight of Al.

Example 4

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) was added 465 g ofpropylene glycol monomethyl ether and dispersed therein to form aslurry, and a solution of 0.5 g of a hydrate of sodium phosphor vanadomolybdate (Na₄PV₁Mo₁₁O₄₀) in 30 g of water was gradually added whilestirring the slurry, and the resultant was stirred for 30 minutes whilemaintaining the slurry temperature at 40° C. Thereafter, 10.0 g oftetraethoxysilane was added, then 8.0 g of N,N-dimethylethanolamine and6.0 g of distilled water were added, and the resultant was stirred for 1hour. Thereafter, the resultant was heated to a temperature of 100° C.and stirred for 12 hours. Furthermore, 5.0 g of3-methacryloxypropyltrimethoxysilane previously hydrolyzed by an aqueous1 mol/L acetic acid solution was added and the resultant was stirred for8 hours. After the completion of the reaction, the obtained slurry wasfiltered after cooling, thereby obtaining an aluminum pigmentcomposition having a nonvolatile content of 58%. The content of eachelement in this aluminum pigment composition was measured in the samemanner as Example 1, and it was found that the content of V was 0.01parts by weight, the content of Mo was 0.18 parts by weight, and thecontent of Si was 1.43 parts by weight, based on 100 parts by weight ofAl.

Example 5

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) was added 465 g ofethylene glycol monobutyl ether and dispersed therein to form a slurry,and 1.0 g of a hydrate of ammonium phosphor vanado molybdate((NH₄)₄PV₁Mo₁₁O₄₀) was added in the state of being dispersed in 30 g ofwater while stirring the slurry, and stirred for 30 minutes whilemaintaining the slurry temperature at 40° C. Thereafter, 16.0 g of 25%ammonia water was added thereto, and the resultant was stirred for 1hour. Thereafter, 10.0 g of tetraethoxysilane and 5.0 g of3-glycidoxypropyltrimethoxysilane were further added thereto, and theresultant was stirred for 2 hours. Thereafter, the resultant was heatedto a temperature of 150° C. and stirred for 6 hours. After thecompletion of the reaction, the obtained slurry was filtered aftercooling, thereby obtaining an aluminum pigment composition having anonvolatile content of 61%. The content of each element in this aluminumpigment composition was measured in the same manner as Example 1, and itwas found that the content of V was 0.02 parts by weight, the content ofMo was 0.35 parts by weight, and the content of Si was 1.45 parts byweight, based on 100 parts by weight of Al.

Example 6

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) were added aditridecylamine salt of phosphotungstomolybdic acid (H₃PW₆Mo₆O₄₀)(mixture of branched isomers) and 2,6-di-t-butyl-p-cresol so that theamounts of the salt and the cresol were 3.0 parts by weight and 0.5parts by weight, respectively, based on 100 parts by weight of analuminum metal component in the aluminum paste, and the resultant waskneaded at 70° C. for 6 hours.

To 135 g of the obtained aluminum particle composition was added 465 gof ethylene glycol monobutyl ether, and the resultant was stirred for 30minutes while maintaining the slurry temperature at 70° C. Thereafter,10.0 g of tetraethoxysilane was added, then 3.2 g of 25% ammonia waterand 5.2 g of distilled water were added, and the resultant was stirredfor additional 2 hours. Thereafter, the resultant was heated to atemperature of 140° C. and stirred for 4 hours. After the completion ofthe reaction, the obtained slurry was filtered after cooling, therebyobtaining an aluminum pigment composition having a nonvolatile contentof 60%. The content of each element in this aluminum pigment compositionwas measured in the same manner as Example 1, and it was found that thecontent of W was 1.00 part by weight, the content of Mo was 0.51 partsby weight, and the content of Si was 1.05 parts by weight, based on 100parts by weight of Al.

Example 7

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) was added aditridecylamine salt of phosphotungstomolybdic acid (H₃PW₆Mo₆O₄₀)(mixture of branched isomers) so that the amount of the salt was 1.0part by weight based on 100 parts by weight of an aluminum metalcomponent in the aluminum paste, and the resultant was kneaded at 70° C.for 6 hours.

To 135 g of the obtained aluminum particle composition was added 465 gof ethylene glycol monobutyl ether, and the resultant was stirred for 30minutes while maintaining the slurry temperature at 70° C. Thereafter,5.0 g of tetraethoxysilane and 5.0 g of 3-aminopropyl trimethoxysilanewere further added, then 5.2 g of distilled water was added, and theresultant was stirred for additional 2 hours. Thereafter, the resultantwas heated to a temperature of 140° C. and stirred for 4 hours. Afterthe completion of the reaction, the obtained slurry was filtered aftercooling, thereby obtaining an aluminum pigment composition having anonvolatile content of 60%. The content of each element in this aluminumpigment composition was measured in the same manner as Example 1, and itwas found that the content of W was 0.28 parts by weight, the content ofMo was 0.13 parts by weight, and the content of Si was 0.9 parts byweight, based on 100 parts by weight of Al.

Example 8

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) was added amonooctylamine salt of phosphotungstomolybdic acid (H₃PW₆Mo₆O₄₀) so thatthe amount of the salt was 2.0 parts by weight based on 100 parts byweight of an aluminum metal component in the aluminum paste, and theresultant was stirred at 70° C. for 6 hours.

To 135 g of the obtained aluminum particle composition was added 465 gof ethylene glycol monobutyl ether, and the resultant was stirred for 30minutes while maintaining the slurry temperature at 40° C. Thereafter,8.0 g of triethanolamine was added and the resultant was stirred for 1hour. Thereafter, 5.0 g of tetraethoxysilane and 5.0 g ofhexyltrimethoxysilane were further added, then 5.5 g of distilled waterwas added, and the resultant was stirred for 2 hours. Thereafter, theresultant was heated to a temperature of 140° C. and stirred for 6hours. After the completion of the reaction, the obtained slurry wasfiltered after cooling, thereby obtaining an aluminum pigmentcomposition having a nonvolatile content of 62%. The content of eachelement in this aluminum pigment composition was measured in the samemanner as Example 1, and it was found that the content of W was 0.75parts by weight, the content of Mo was 0.40 parts by weight, and thecontent of Si was 1.10 parts by weight, based on 100 parts by weight ofAl.

Example 9

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) were added anN,N-dimethylethanolamine salt of phosphovanadomolybdic acid(H₄PV₁Mo₁₁O₄₀) and ascorbic acid so that the amounts of the salt and theascorbic acid were 1.0 part by weight and 0.5 parts by weight,respectively, based on 100 parts by weight of an aluminum metalcomponent in the aluminum paste, and the resultant was stirred at 70° C.for 6 hours.

To 135 g of the obtained aluminum particle composition was added 465 gof ethylene glycol monobutyl ether, and the resultant was stirred for 30minutes while maintaining the slurry temperature at 70° C. Thereafter,5.0 g of tetraethoxysilane and 5.0 g of phenyltrimethoxysilane wereadded in the state of being previously hydrolyzed by an aqueous 1 mol/Lacetic acid solution, and the resultant was heated to a temperature of130° C. and stirred for 12 hours. After the completion of the reaction,the obtained slurry was filtered after cooling, thereby obtaining analuminum pigment composition having a nonvolatile content of 52%. Thecontent of each element in this aluminum pigment composition wasmeasured in the same manner as Example 1, and it was found that thecontent of V was 0.02 parts by weight, the content of Mo was 0.45 partsby weight, and the content of Si was 1.07 parts by weight, based on 100parts by weight of Al.

Example 10

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3160 (average particlediameter: 16 μm, nonvolatile content: 74%)”) were added 465 g of tolueneand 4.0 g of N,N-dimethylbenzylamine, and the resultant was stirred for30 minutes while maintaining the slurry temperature at 50° C.Thereafter, 2.0 g of dimethyldichlorosilane was added and the resultantwas stirred for 18 hours. Thereafter, a solution of 1.0 g of a hydrateof silicotungstomolybdic acid (H₄SiW₃Mo₉O₄₀) in 30 g of isopropanol wasgradually added and the resultant was stirred for 6 hours. Thereafter,the resultant was heated to a temperature of 100° C., and 5.0 g oftetraethoxysilane and 2.5 g of N-methyl-3-aminopropyl-trimethoxysilanepreviously hydrolyzed by 1 mol/L hydrochloric acid were added and theresultant was stirred for 6 hours. After the completion of the reaction,the obtained slurry was filtered after cooling, thereby obtaining analuminum pigment composition having a nonvolatile content of 65%. Thecontent of each element in this aluminum pigment composition wasmeasured in the same manner as Example 1, and it was found that thecontent of W was 0.17 parts by weight, the content of Mo was 0.26 partsby weight, and the content of Si was 1.15 parts by weight, based on 100parts by weight of Al.

Example 11

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3160 (average particlediameter: 16 μm, nonvolatile content: 74%)”) was added 465 g of ethyleneglycol monobutyl ether and dispersed therein to form a slurry, and 0.5 gof a hydrate of phosphovanadomolybdic acid (H₄PV₁Mo₁₁O₄₀) was addedwhile stirring the slurry, and the resultant was stirred for 2 hourswhile maintaining the slurry temperature at 70° C. Thereafter, 5.0 g oftetraethoxysilane was added and then the resultant was stirred for 8hours. During this operation, 5.0 g of an aqueous phosphoric acidsolution diluted to 20% was continuously added over 2 hours. After thecompletion of the reaction, the obtained slurry was filtered aftercooling, thereby obtaining an aluminum pigment composition having anonvolatile content of 60%.

The content of each element in this aluminum pigment composition wasmeasured in the same manner as Example 1, and it was found that thecontent of V was 0.01 parts by weight, the content of Mo was 0.20 partsby weight, and the content of Si was 0.60 parts by weight, based on 100parts by weight of Al.

Example 12

Polyphosphoric acid (2.0 parts by weight) was added based on 100 partsby weight of an aluminum metal component in the aluminum pigmentcomposition obtained in Example 11, and the resultant was kneaded at 40°C. for 2 hours to obtain an aluminum pigment composition.

Example 13

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3160 (average particlediameter: 16 μm, nonvolatile content: 74%)”) was added a triethanolaminesalt of silicotungstomolybdic acid (H₄SiW₃Mo₉O₄₀) so that the amount ofthe salt was 1.0 part by weight based on 100 parts by weight of analuminum metal component in the aluminum paste, and was also added 5.0parts by weight of a methoxy-modified methylphenylsilicone oligomer(produced by Shin-Etsu Chemical Co., Ltd., trade name “KR-213”) and theresultant was kneaded at 70° C. for 12 hours to obtain an aluminumpigment composition. The content of each element in this aluminumpigment composition was measured in the same manner as Example 1, and itwas found that the content of W was 0.22 parts by weight, the content ofMo was 0.39 parts by weight, and the content of Si was 0.90 parts byweight, based on 100 parts by weight of Al.

Comparative Example 1

The same procedure as Example 1 was performed except that the step ofadding tetraethoxysilane was not used, thereby obtaining an aluminumpigment composition having a nonvolatile content of 73%. The content ofeach element in this aluminum pigment composition was measured in thesame manner as Example 1, and it was found that the content of W was0.32 parts by weight, the content of Mo was 0.16 parts by weight, andthe content of Si was 0.00 parts by weight, based on 100 parts by weightof Al.

Comparative Example 2

The same procedure as Example 1 was performed except that the step ofadding a hydrate of phosphotungstomolybdic acid (H₃PW₆Mo₆O₄₀) was notused, thereby obtaining an aluminum pigment composition having anonvolatile content of 60%. The content of each element in this aluminumpigment composition was measured in the same manner as Example 1, and itwas found that the content of W was 0.00 parts by weight, the content ofMo was 0.00 parts by weight, and the content of Si was 0.40 parts byweight, based on 100 parts by weight of Al.

Comparative Example 3

The same procedure as Example 1 was performed except that,phosphomolybdic acid was added instead of 1.0 g of a hydrate ofphosphotungstomolybdic acid (H₃PW₆Mo₆O₄₀), 0.8 g of a hydrate of phosphomolybdic acid (H₃PMo₁₂O₄₀) which is the same molar number was added,thereby obtaining an aluminum pigment composition having a nonvolatilecontent of 61%. The content of each element in this aluminum pigmentcomposition was measured in the same manner as Example 1, and it wasfound that the content of Mo was 0.30 parts by weight and the content ofSi was 1.00 part by weight, based on 100 parts by weight of Al.

Comparative Example 4

A commercially available aluminum paste (produced by Asahi KaseiChemicals Corporation, trade name “GX-3100 (average particle diameter:10.5 μm, nonvolatile content: 74%)”) was used as it is to prepare ametallic coating as described below.

Example 14

To 167 g of the aluminum pigment composition obtained in Example 1 wasadded 700 g of mineral spirit and dispersed therein to form a slurry,and the slurry was stirred for 30 minutes while maintaining the slurrytemperature at 70° C. Then, 0.75 g of acrylic acid was added and theresultant was stirred for 30 minutes. Thereafter, 5.6 g oftrimethylolpropane triacrylate (TMPTA), 2.4 g of di-trimethylolpropanetetraacrylate (DTMPTA) and 3.0 g of2,2′-azobis-2,4-dimethylvaleronitrile (ADVN) were dissolved in 80 g ofmineral spirit, and the obtained solution was added over 3 hours.Thereafter, stirring was continued for additional 2 hours. After thecompletion of the reaction, the obtained slurry was filtered aftercooling, thereby obtaining 200 g of an aluminum pigment compositionhaving a nonvolatile content of 55%.

Example 15

Tridecyl acid phosphate (3.0 parts by weight) was added based on 100parts by weight of an aluminum metal component in the aluminum pigmentcomposition obtained in Example 14, and the resultant was kneaded at 40°C. for 2 hours to obtain an aluminum pigment composition.

Example 16

The same procedure as Example 11 was performed except that 167 g of thealuminum pigment composition obtained in Example 1 was changed to 182 gof the aluminum pigment composition obtained in Example 2, 0.75 g ofacrylic acid was changed to 1.50 g of 2-isocyanatoethyl acrylate, and1.0 g of benzyl acrylate was added in addition to TMPTA and DTMPTA,thereby obtaining 213 g of an aluminum pigment composition having anonvolatile content of 52.1%.

Example 17

To 172 g of the aluminum pigment composition obtained in Example 3 wasadded 700 g of mineral spirit and dispersed therein to form a slurry,and the slurry was stirred for 30 minutes while maintaining the slurrytemperature at 70° C. Thereafter, 5.6 g of TMPTA, 2.4 g of DTMPTA and3.0 g of ADVN were dissolved in 80 g of mineral spirit, and the obtainedsolution was added over 3 hours. Thereafter, stirring was continued foradditional 2 hours. After the completion of the reaction, the obtainedslurry was filtered after cooling, thereby obtaining 195 g of analuminum pigment composition having a nonvolatile content of 56%.

Example 18

The same procedure as Example 11 was performed except that 167 g of thealuminum pigment composition obtained in Example 1 was changed to 164 gof the aluminum pigment composition obtained in Example 4, DTMPTA waschanged to pentaerythritol tetraacrylate, and 1.0 g of divinylbenzenewas further added, thereby obtaining 189 g of an aluminum pigmentcomposition having a nonvolatile content of 58.4%.

Example 19

To 135 g of a commercially available aluminum paste (produced by AsahiKasei Chemicals Corporation, trade name “GX-3100 (average particlediameter: 10.5 μm, nonvolatile content: 74%)”) were added aditridecylamine salt of phosphotungstomolybdic acid (H₃PW₆Mo₆O₄₀) and2,6-di-t-butyl-p-cresol so that the amounts of the salt and the cresolwere 3.0 parts by weight and 0.5 parts by weight, respectively, based on100 parts by weight of an aluminum metal component in the aluminumpaste, and the resultant was kneaded at 70° C. for 6 hours.

The same procedure as Example 11 was performed except that thisresultant was used instead of the aluminum pigment composition obtainedin Example 1, 0.75 g of acrylic acid was changed to 2.0 g of2-acryloyloxyethyl acid phosphate, 5.6 g of TMPTA was changed to 2.8 gof trimethylolpropane trimethacrylate, the amount of DTMPTA was changedfrom 2.4 g to 1.2 g, and 1.0 g of glycidyl methacrylate was furtheradded, thereby obtaining 189 g of an aluminum pigment composition havinga nonvolatile content of 57.3%.

Examples 20 to 38 Comparative Examples 5 to 8

With respect to the aluminum pigment compositions obtained in Examples 1to 19, and the aluminum pigment compositions obtained in ComparativeExamples 1 to 4, water-based metallic coatings each having the followingcomposition were prepared. Herein, the results thereof were defined asExamples 22 to 42 and Comparative Examples 5 to 8.

[Preparation of Water-Based Metallic Coatings]

Water-based metallic coatings each having the following components wereprepared.

Aluminum pigment composition: 12.0 g as nonvolatile content

Diethylene glycol monobutyl ether: 18.0 g

Polyoxyethylene lauryl ether (non-ionic surfactant)

(produced by Matsumoto Yushi-Seiyaku Co., Ltd., trade name “ActinolL5”): 6.0 g

Distilled water: 12.0 g

Acrylic emulsion (acid value: 13 mgKOH/g, hydroxyl value: 40 mgKOH/g,

Tg: 20° C., solid content: 42%, number average molecular weight:100,000, pH: 8.4): 240 g

The above components were mixed, and then the pH was adjusted from 7.7to 7.8 by ammonia water and the viscosity was adjusted from 650 to 750mPa·s (Brookfield-type viscometer, No. 3 rotor, 60 rpm, 25° C.) by acarboxylic acid-type thickening agent and distilled water.

The prepared water-based metallic coatings were used to perform thefollowing evaluations.

[Evaluation 1 (Coating Stability)]

The coatings prepared by the above formulation were visually evaluatedin terms of changes in state after being left to stand at 23° C. for 24hours.

-   -   ◯: no change was particularly observed.    -   Δ: aggregation of aluminum pigments was slightly observed.    -   x: aggregation of aluminum pigments was observed.

[Evaluation 2 (Storage Stability (Gas Generation) Evaluation)]

Each water-based metallic coating (200 g) was taken in a flask, theflask was placed in a constant temperature water bath at 40° C., and thecumulative amount of hydrogen gas generated was observed until theelapse of 24 hours. The following criteria were used to evaluate theamount of the gas generated, and were assumed to be an index of storagestability in each coating.

-   -   {circle around (o)}: 0 ml in the range of experimental error        (±about 0.5 ml)    -   ◯: less than 1.0 ml    -   Δ: 1.0 ml or more and less than 5.0 ml    -   x: 5.0 ml or more and less than 20 ml    -   x x: 20 ml or more

[Evaluation 3 (Coating Film Color Tone Evaluation)]

The above coatings were used to form coating films, and each film wasevaluated for brightness and flip-flop feeling.

<Brightness>

Brightness was evaluated by using a laser-type metallic feelingmeasuring apparatus manufactured by Kansai Paint Co., Ltd., AlcopeLMR-200. The apparatus includes a laser light source having an incidentangle of 45 degrees, a light receiver having an acceptance angle of 0degrees and a light receiver having an acceptance angle of −35 degreesas optical conditions. With respect to a measurement value, an IV valuewas determined at an acceptance angle of −35 degrees, where the maximumintensity of light is obtained, in the reflected laser light subtractedby the light in the specular reflection region where the laser light isreflected on the surface of the coating film. The IV value is aparameter which is proportional to the intensity of regularly reflectedlight from the coating film, and indicates the magnitude of brightnessof light. The judging criteria are as follows.

-   -   {circle around (o)}: higher than Comparative Example 5 by 20 or        more    -   ◯: difference from Comparative Example 5 being +10 to 20    -   Δ: difference from Comparative Example 5 being less than ±10    -   x: lower than Comparative Example 5 by 10 or more

<Flip-Flop Feeling (FF)>

Flip-flop feeling was evaluated by using a variable angle color metermanufactured by Suga Test Instruments Co., Ltd. An F/F value wasdetermined from the slopes of the logarithms of the reflected lightintensities (L values) at observation angles (acceptance angles) of 30degrees and 80 degrees against a light source having an incident angleof 45 degrees. The F/F value is a parameter which is proportional to theorientation degree of a metallic pigment, and indicates the magnitude ofthe flip-flop feeling of the pigment. The judging criteria are asfollows.

-   -   {circle around (o)}: higher than Comparative Example 5 by 0.1 or        more    -   ◯: difference from Comparative Example 5 being +0.05 to 0.1    -   Δ: difference from Comparative Example 5 being less than ±0.05    -   x: lower than Comparative Example 5 by 0.05 or more

<Hiding Power>

Coating films each applied on a PET sheet were visually judged.

-   -   ◯: more excellent than standard    -   x: equal to or less excellent than standard

[Evaluation 4 (Evaluation of Discoloration Resistance of Dye)]

To 5 g of each aluminum pigment composition was added 20 ml of anaqueous methylene blue solution (0.04 mmol/L), and warmed at 40° C. for24 hours. Then, this solution was filtered and visually evaluated forthe degree of discoloration of blue color.

-   -   ◯: No remarkable discoloration was observed.    -   Δ: Slight discoloration was observed.    -   x: decoloration was observed.

The results of Evaluations 1 to 4 are shown in Table 1.

TABLE 1 Evaluation 4 Pigment Evaluation 1 Evaluation 2 Evaluation 3Discoloration composition Coating Storage Hiding resistance usedstability stability Brightness FF power of dye Example 20 Example 1  ◯ ◯⊚ ⊚ ◯ ◯ Example 21 Example 2  ◯ ⊚ ⊚ ⊚ ◯ ◯ Example 22 Example 3  ◯ ⊚ ⊚ ⊚◯ ◯ Example 23 Example 4  ◯ ◯ ⊚ ◯ ◯ ◯ Example 24 Example 5  ◯ ◯ ◯ ⊚ ◯ ◯Example 25 Example 6  ◯ ⊚ ⊚ ⊚ ⊚ ◯ Example 26 Example 7  ◯ ◯ ◯ ◯ ◯ ◯Example 27 Example 8  ◯ ⊚ ⊚ ⊚ ⊚ ◯ Example 28 Example 9  ◯ ◯ ⊚ ⊚ ⊚ ◯Example 29 Example 10 ◯ ◯ ◯ ◯ ◯ ◯ Example 30 Example 11 ◯ ◯ ⊚ ⊚ ◯ ◯Example 31 Example 12 ◯ ⊚ ◯ ◯ ◯ ◯ Example 32 Example 13 ◯ ◯ ◯ ◯ ◯ ◯Example 33 Example 14 ◯ ⊚ ◯ ◯ ◯ ◯ Example 34 Example 15 ◯ ⊚ ◯ ⊚ ◯ ◯Example 35 Example 16 ◯ ⊚ ⊚ ⊚ ◯ ◯ Example 36 Example 17 ◯ ⊚ ◯ ◯ ◯ ◯Example 37 Example 18 ◯ ⊚ ◯ ◯ ◯ ◯ Example 38 Example 19 ◯ ⊚ ◯ ◯ ◯ ◯Comparative Comparative Δ X 450 1.8 Standard Δ Example 5 Example 1Comparative Comparative Δ X X Δ X ◯ Example 6 Example 2 ComparativeComparative ◯ Δ Δ Δ X X Example 7 Example 3 Comparative Comparative X XX X X X ◯ Example 8 Example 4

Examples 39 to 44 Comparative Example 9

With respect to the aluminum pigment compositions containing an organicoligomer or polymer, obtained in Examples 14 to 19 and ComparativeExample 1, the following adhesion and chemical resistance tests wereperformed. Herein, the results thereof were defined as Examples 39 to 44and Comparative Example 9.

[Preparation of Metallic Coating]

Metallic coatings each having the following components were prepared.

Aluminum pigment composition: 5 g as a nonvolatile content Thinner(produced by Musashi Paint Co., Ltd., trade name “Pla Ace thinner No.2726”): 50 g

Acrylic resin (produced by Musashi Paint Co., Ltd., trade name “Pla AceNo. 7160”): 33 g

[Evaluation]

An ABS resin plate was coated with each prepared metallic coating byusing an air-spray apparatus so that the thickness of a film to be driedwas 10 μm, and dried in an oven at 60° C. for 30 minutes to obtain acoated plate for evaluation.

The coated plate for evaluation was used to perform the followingevaluation.

[Evaluation 5 (Adhesion)]

Cellotape (registered trademark, manufactured by Nichiban Co., Ltd.,CT-24) was adhered to the coating film on the coated plate forevaluation and pulled at an angle of 45 degrees, and the degree of thealuminum pigment particles peeled was visually observed. The judgingcriteria are as follows.

-   -   ◯: no peeling    -   Δ: slightly peeling    -   x: peeling

[Evaluation 6 (Chemical Resistance)]

The lower half of the coated plate for evaluation was immersed in abeaker into which an aqueous 0.1 N—NaOH solution was loaded, and left tostand at 55° C. for 4 hours. The coated plate after testing was washedwith water and dried, and then colors of the immersed portion and theunimmersed portion were measured under Condition d (8-d method) ofJIS-Z-8722 (1982) to determine color difference ΔE according to 6.3.2 ofJIS-Z-8730 (1980). The judging was as follows depending on values ofcolor difference ΔE. (The smaller values are more favorable.)

-   -   ◯: less than 1.0    -   x: 1.0 or more

The results are shown in Table 2.

TABLE 2 Pigment Evaluation 6 composition Evaluation 5 Chemical usedAdhesion resistance Example 39 Example 14 ◯ ◯ Example 40 Example 15 ◯ ◯Example 41 Example 16 ◯ ◯ Example 42 Example 17 ◯ ◯ Example 43 Example18 ◯ ◯ Example 44 Example 19 ◯ ◯ Comparative Comparative X X Example 9Example 1

INDUSTRIAL APPLICABILITY

The present invention can provide a metallic pigment composition thatcan be used in coating compositions, ink compositions or the like, inparticular, water-based coatings, water-based inks or the like, that isexcellent in storage stability of coatings with less deterioration inphotoluminescence, hiding power, flip-flop feeling and the like whenforming a coating film.

1. A metallic pigment composition comprising one or moremixed-coordination type heteropolyanion compounds, a hydrolysate of asilicon-containing compound and/or a condensate thereof, and metallicparticles, wherein a heteroatom constituting the mixed-coordination typeheteropolyanion compound is at least one selected from elements of GroupIIIB, Group IVB, and Group VB, and wherein a polyatom constituting themixed-coordination type heteropolyanion compound is selected fromtransition metals.
 2. The metallic pigment composition according toclaim 1, further comprising at least one selected from the groupconsisting of an organic oligomer or polymer.
 3. The metallic pigmentcomposition according to claim 1 or 2, further containing one or moreselected from the group consisting of (i) inorganic phosphoric acids orsalts thereof; and (ii) acidic organic phosphoric or phosphorous acidesters or salts thereof.
 4. The metallic pigment composition accordingto claim 1, wherein the metallic particles are made of aluminum. 5.(canceled)
 6. (canceled)
 7. (canceled)
 8. (canceled)
 9. The metallicpigment composition according to claim 1, wherein the mixed-coordinationtype heteropolyanion compound is at least one mixed-coordination typeheteropoly acid selected from H₃PW_(x)Mo_(12-x)O₄₀.nH₂O(phosphotungstomolybdic acid.n-hydrate), H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O(phosphovanadomolybdic acid.n-hydrate), H₄SiW_(x)Mo_(12-x)O₄₀.nH₂O(silicotungstomolybdic acid.n-hydrate), andH_(4+x)SiV_(x)Mo_(12-x)O₄₀.nH₂O (silicovanadomolybdic acid.n-hydrate);and 1≦x≦11 and n≧0.
 10. The metallic pigment composition according toclaim 1, wherein the mixed-coordination type heteropolyanion compound isa salt of a mixed-coordination type heteropoly acid with at least oneselected from alkali metals, alkaline earth metals, ammonia, and aminecompounds represented by the following general formula (1):

wherein R1, R2 and R3 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R1 and R2 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, or are taken together with a nitrogen atom to form a 5-memberedor 6-membered ring that is capable of additionally containing a nitrogenor oxygen atom as a crosslinking member, or R1, R2 and R3 are takentogether to form a multi-membered multiring composition that is capableof containing one or more additional nitrogen atoms and/or oxygen atomsas a crosslinking member, and R1, R2 and R3 are not a hydrogen atom atthe same time and n represents a numerical value of 1 to
 2. 11. Themetallic pigment composition according to claim 10, wherein themixed-coordination type heteropoly acid is at least onemixed-coordination type heteropoly acid selected fromH₃PW_(x)Mo_(12-x)O₄₀.nH₂O (phosphotungstomolybdic acid.n-hydrate),H_(3+x)PV_(x)Mo_(12-x)O₄₀.nH₂O (phosphovanadomolybdic acid.n-hydrate),H_(4+x)SiW_(x)Mo_(12-x)O₄₀.nH₂O (silicotungstomolybdic acid.n-hydrate),and H₄SiW_(x)Mo_(12-x).nH₂O (silicovanadomolybdic acid.n-hydrate); and1≦x≦11 and n≧0.
 12. (canceled)
 13. (canceled)
 14. The metallic pigmentcomposition according to claim 1, wherein the silicon-containingcompound is at least one selected from compounds represented by thefollowing general formula (2), (3), (4) or (5) and a partial condensatethereof:[Formula 2]R4mSi(OR5)4-m  (2) wherein R4 is a hydrogen atom or a hydrocarbon grouphaving 1 to 30 carbon atoms that may optionally contain a halogen group,R5 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms,R4 and R5 may be the same or different, and when the numbers of R4 andR5 are each two or more, each of R4 and R5 may be the same, may bepartially the same, or may be all different; and 1≦m≦3;[Formula 3]R6pR7qSi(OR8)4-p-q  (3) wherein R6 is a group containing a reactivegroup that can be chemically bound to other functional group, R7 is ahydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms thatmay optionally contain a halogen group, R8 is a hydrogen atom or ahydrocarbon group having 1 to 8 carbon atoms, and when the numbers ofR6, R7 and R8 are each two or more, each of R6, R7 and R8 may be thesame, may be partially the same, or may be all different; and 1≦p≦3,0≦q≦2, and 1≦p+q≦3;[Formula 4]Si(OR9)4  (4) wherein R9 is each a hydrogen atom or a hydrocarbon grouphaving 1 to 8 carbon atoms, and when the number of R9 is two or more,each of R9 may be the same, may be partially the same, or may be alldifferent; and[Formula 5]R10rSiCl4-r  (5) wherein R10 is a hydrogen atom or a hydrocarbon grouphaving 1 to 30 carbon atoms that may optionally contain a halogen group,and when the number of R10 is two or more, each of R10 may be the same,may be partially the same, or may be all different; and 0≦r≦3.
 15. Themetallic pigment composition according to claim 2, wherein the organicoligomer or polymer is an acrylic resin and/or a polyester resin. 16.The metallic pigment composition according to claim 3, wherein theinorganic phosphoric acids are at least one selected fromorthophosphoric acid, metaphosphoric acid, pyrophosphoric acid,triphosphoric acid, tetraphosphoric acid, and phosphorous acid, andwherein the inorganic phosphoric acid salts are salts of the inorganicphosphoric acids with at least one selected from alkali metals, alkalineearth metals, ammonia, and amines represented by the following generalformula (6):

wherein R11, R12 and R13 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R11 and R12 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, R11 and R12 are optionally taken together with a nitrogen atom toform a 5-membered or 6-membered ring that is capable of additionallycontaining a nitrogen or oxygen atom as a crosslinking member, or R11,R12 and R13 are optionally taken together to form a multi-memberedmultiring that is capable of containing one or more additional nitrogenatoms and/or oxygen atoms as a crosslinking member, and R11, R12 and R13are not a hydrogen atom at the same time; and n represents a numericalvalue of 1 to
 2. 17. (canceled)
 18. The metallic pigment compositionaccording to claim 3, wherein the acidic organic phosphoric orphosphorous acid esters are at least one or more selected from compoundsrepresented by the following general formula (7):

wherein R14, R15 and R16 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, or a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, one or twoof R14, R15 and R16 are a hydrogen atom, and the total number of carbonatoms of R14, R15 and R16 is 4 or more; and m represents a numericalvalue of 0 or 1; and wherein the acidic organic phosphoric orphosphorous acid ester salts are salts of phosphoric acid estersrepresented by the following general formula (7) with at least oneselected from alkali metals, alkaline earth metals, ammonia, and aminesrepresented by the following general formula (6):

wherein R14, R15 and R16 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, or a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, one or twoof R14, R15 and R16 are a hydrogen atom, and the total number of carbonatoms of R14, R15 and R16 is 4 or more; and m represents a number of 0or 1; and

wherein R11, R12 and R13 may be the same or different, and are each ahydrogen atom, or a mono or divalent hydrocarbon group having 1 to 30carbon atoms that may optionally contain an ether bond, an ester bond, ahydroxyl group, a carbonyl group, and a thiol group, R11 and R12 areoptionally taken together to form a 5-membered or 6-membered cycloalkylgroup, R11 and R12 are optionally taken together with a nitrogen atom toform a 5-membered or 6-membered ring that is capable of additionallycontaining a nitrogen or oxygen atom as a crosslinking member, or R11,R12 and R13 are optionally taken together to form a multi-memberedmultiring that is capable of containing one or more additional nitrogenatoms and/or oxygen atoms as a crosslinking member, and R11, R12 and R13are not a hydrogen atom at the same time; and n represents a numericalvalue of 1 to
 2. 19. (canceled)
 20. The metallic pigment compositionaccording to claim 2, wherein a monomer constituting the organicoligomer or polymer is at least one selected from compounds representedby the following general formula (8):

wherein R17, R18 and R19 may be the same or different, and are each ahydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms that mayoptionally contain an ether group, an ester group, a hydroxyl group, acarbonyl group, and a halogen group, a hydrocarbon group that mayoptionally contain a ring structure or an unsaturated bond, or a grouprepresented by the following general formula (9), one or two of R17, R18and R19 are a hydrogen atom, one or two thereof are the followinggeneral formula (9), and the total number of carbon atoms of R17, R18and R19 is 4 or more; and m represents a numerical value of 0 or 1:

wherein R20 and R23 represent a hydrogen atom or a methyl group, R21 isa trivalent organic group having 2 to 8 carbon atoms that may optionallycontain an oxygen atom, and R22 represents a hydrogen atom or thefollowing general formula (10); and h represents a number of 0 or 1 andi represents a numerical value of 0 to 10:[Formula 12]—CH²X  (10) wherein X represents a hydrogen atom or a chlorine atom. 21.The metallic pigment composition according to claim 1, wherein themixed-coordination type heteropolyanion compound is present in an amountof 0.01 to 10 parts by weight based on 100 parts by weight of themetallic particles.
 22. The metallic pigment composition according toclaim 1, wherein the hydrolysate of a silicon-containing compound and/orthe condensate thereof is present in an amount of 0.01 to 50 parts byweight based on 100 parts by weight of the metallic particles.
 23. Themetallic pigment composition according to claim 2, wherein the organicoligomer or polymer is present in an amount of 0.01 to 50 parts byweight based on 100 parts by weight of the metallic particles.
 24. Themetallic pigment composition according to claim 3, containing at leastone selected from the group consisting of (i) inorganic phosphoric acidsor salts thereof; and (ii) acidic organic phosphoric or phosphorous acidesters or salts thereof in an amount of 0.01 to 20 parts by weight basedon 100 parts by weight of the metallic particles.
 25. A method forproducing the metallic pigment composition according to claim 1,comprising mixing metallic particles with a mixed-coordination typeheteropolyanion compound and a hydrolysate of a silicon-containingcompound and/or a condensate thereof in the presence of a solvent inseparate steps or in a single step.
 26. The production method accordingto claim 25, comprising mixing the metallic particles with themixed-coordination type heteropolyanion compound in the presence of asolvent, and then mixing the resulting mixture with the hydrolysate of asilicon-containing compound and/or the condensate thereof.
 27. A methodfor producing the metallic pigment composition according to claim 2,comprising mixing metallic particles with a mixed-coordination typeanorganic molybdenum compound and a hydrolysate of a silicon-containingcompound and/or a condensate thereof in the presence of a solvent inseparate steps or in a single step, and then polymerizing or mixing anorganic oligomer or polymer.
 28. A coating composition comprising themetallic pigment composition according to claim
 1. 29. An inkcomposition comprising the metallic pigment composition according toclaim
 1. 30. A coating film formed by the coating composition accordingto claim
 28. 31. A printed material formed by the ink compositionaccording to claim 29.